Preparation of isobutene homo- or copolymer derivatives

ABSTRACT

A process for preparing isobutene homo- or copolymer derivatives by (i) polymerizing isobutene or an isobutene-comprising monomer mixture in the presence of an iron halide-donor complex, an aluminum trihalide-donor complex, or an alkylaluminum halide-donor complex, (ii) reacting a resulting high-reactivity isobutene polymer with a compound which introduces a low molecular weight polar group or a substructure thereof, and (iii) in the case of reaction with a substructure, further reacting to complete the formation of the low molecular weight polar group. The homo- or copolymer derivatives include a radical of a hydrophobic polyisobutene polymer having a number-average molecular weight of 110 to 250 000 and low molecular weight polar groups including amino functions, nitro groups, hydroxyl groups, mercaptan groups, carboxylic acid or carboxylic acid derivative functions, sulfonic acid or sulfonic acid derivative functions, aldehyde functions and/or silyl groups.

The present invention relates to an improved process for preparingisobutene homo- or copolymer derivatives. The present invention furtherrelates to novel isobutene homopolymer derivatives.

Isobutene homo- or copolymer derivatives such as polyisobuteneamines orpolyisobutenylsuccinanhydrides are often obtained from so-calledhigh-reactivity isobutene homo- or copolymers. In contrast to so-calledlow-reactivity polymers, high-reactivity isobutene homo- or copolymersare understood to mean those polyisobutenes which comprise a highcontent of terminal ethylenic double bonds (α-double bonds),specifically in practice of 80 mol % or more, based on the individualchain ends of the polyisobutene macromolecules. Vinylidene groups arenormally understood to mean those double bonds whose position in thepolyisobutene macromolecule is described by the general formula

i.e. the double bond is present in an a position in the polymer chain.“Polymer” represents the polyisobutene radical shortened by oneisobutene unit. The vinylidene groups exhibit the highest reactivity,for example in the thermal addition onto sterically demanding reactantssuch as maleic anhydride, whereas a double bond further toward theinterior of the macromolecules in most cases exhibits lower reactivity,if any, in functionalization reactions.

The uses of such high-reactivity polyisobutenes include use asintermediates for preparing additives for lubricants and fuels; forexample, according to the teaching of DE-A 27 02 604, they are reactedwith maleic anhydride to give polyisobutenylsuccinic anhydrides.However, the high-reactivity polyisobutenes obtainable by the process ofDE-A 27 02 604 by cationic polymerization of isobutene in the liquidphase in the presence of boron trifluoride as a catalyst have somedisadvantages; for example they have a relatively high polydispersity.The polydispersity is a measure of the molecular weight distribution ofthe resulting polymer chains and corresponds to the quotient ofweight-average molecular weight M_(w) and number-average molecularweight M_(n) (PDI=M_(w)/M_(n)).

Polyisobutenes with a similarly high proportion of terminal double bondsbut with a narrower molecular weight distribution are, for example,obtainable by the process of EP-A 145 235, U.S. Pat. No. 5,408,018 andWO 99/64482, the polymerization being effected in the presence of adeactivated catalyst, for example of a complex of boron trifluoride withalcohols and/or ethers.

High-reactivity polyisobutenes are also obtainable by living cationicpolymerization of isobutene and subsequent dehydrohalogenation of theresulting polymerization product, for example by the process from U.S.Pat. No. 5,340,881. However, such a process is complex since the halogenend group introduced with the living cationic polymerization has to beeliminated in a separate step in order to generate the double bond.

It has additionally been known for some time that the Lewis acidaluminum trichloride can also be used as a polymerization catalyst forisobutene, for example from High Polymers, volume XXIV (part 2), p.713-733 (editor: Edward C. Leonard), J. Wiley & Sons publishers, NewYork, 1971.

The European patent application with the reference number 10157068.7,which was yet to be published at the priority date of the presentapplication, describes a process for preparing high-reactivity isobutenehomo- or copolymers by polymerization in the presence of an aluminumtrihalide-donor complex which is effective as a polymerization catalystor of an alkyl aluminum halide-donor complex which comprises, as thedonor, an organic compound with at least one ether function or acarboxylic ester function, and optionally an organic hydroxyl compound,an organic halogen compound or water as an initiator. Further reactionswith the high-reactivity isobutene homo- or copolymers thus prepared arenot described therein.

CN 101955558 A discloses that iron(III) chloride is suitable as acoinitiator in the cationic isobutene polymerization for preparation ofhigh-reactivity polyisobutenes and copolymers thereof. The initiatorsrecommended are water, phenols, protic acids such as sulfuric acid,tertiary alcohols, tertiary chlorides, tertiary carboxylic esters andcarboxylic acids themselves. The complexing agents mentioned for thesystems which initiate the polymerization are especially alkyl ethers.

However, the derivatization methods known from the prior art forhigh-reactivity isobutene homo- or copolymers, for example to preparepolyisobutenylsuccinic anhydrides according to the teaching of DE-A 2702 604, have a series of deficiencies. For instance, the content ofterminal vinylidene double bonds in the precursor is still too low. Theyields in the conversion to the derivatives are in need of improvement.The appearance and the consistency of the derivatives, especially thesuppression of discoloration, for example caused by undesiredcarbonization reactions in the course of thermal stress duringderivatization, are still not optimal. Moreover, the physical propertiesof the derivatives, especially the viscosity behavior at lowtemperatures, as can occur, for example, in practical use in lubricantoils, and the solubility, especially in polar media, the thermalstability and the storage stability of the additives are still in needof improvement. The derivatization processes known from the prior artfor isobutene polymers which proceed from isobutene polymers prepared bymeans of fluorinated polymerization catalysts have the disadvantage thatthey trigger corrosion on numerous metallic materials and steel typesowing to the residual fluorine content.

It was an object of the present invention, proceeding fromhigh-reactivity isobutene homo- or copolymers, to provide an improvedprocess for preparing isobutene homo- or copolymer derivatives, which nolonger has the deficiencies of the prior art. More particularly, theisobutene homo- or copolymer derivatives should be preparable fromisobutene polymers with a high content of terminal vinylidene doublebonds, especially at least 50 mol %, preferably at least 60 mol %,preferably at least 70 mol %, preferably at least 80 mol %, preferablyat least 85 mol %, more preferably at least 90 mol %, and in acceptableyields. In addition, appearance and consistency of the derivatives, forexample the color thereof, should be improved. In addition, the physicalproperties of the derivatives, especially the viscosity behavior at lowtemperatures, and the solubilities, especially in polar media, thethermal stability and the storage stability of the derivatives should beimproved. Any catalyst system used to obtain the isobutene polymers inthe precursor should be sufficiently active, have a long life, and beunproblematic in terms of handling and not be susceptible to faults;more particularly, it should be free of fluorine in order to preventcorrosion on metallic materials and steel types caused by residualfluorine content.

The object is achieved by a process for preparing isobutene homo- orcopolymer derivatives of the general formula I

POL(-A)_(n)   (I)

in which

POL denotes the n-functional radical of a hydrophobic polyisobutenehomo- or copolymer which has a number-average molecular weight (Me) of110 to 250 000 and may comprise incorporated structural units formedfrom mono-, di- or trifunctional initiators,

A is a low molecular weight polar group which in each case comprises oneor more amino functions and/or nitro groups and/or hydroxyl groupsand/or mercaptan groups and/or carboxylic acid or carboxylic acidderivative functions, especially succinic anhydride or succinic acidderivative functions, and/or sulfonic acid or sulfonic acid derivativefunctions and/or aldehyde functions and/or silyl groups, and

the variable n is 1, 2 or 3, where the variables A may be the same ordifferent when n=2 and n=3,

which comprises polymerizing isobutene or an isobutene-comprisingmonomer mixture in the presence

-   -   (A) of an iron halide-donor complex effective as a        polymerization catalyst, of an aluminum trihalide-donor complex        or of an alkylaluminum halide-donor complex which comprises, as        the donor, an organic compound with at least one ether function        or a carboxylic ester function, or    -   (B) of at least one Lewis acid suitable as a polymerization        catalyst or of a complex which is effective as a polymerization        catalyst and is formed from at least one Lewis acid and at least        one donor, and in the presence of at least one initiator, using        as the at least one initiator an organic sulfonic acid of the        general formula Z—SO₃H in which the variable Z denotes a C₁- to        C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to        C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or C₇- to        C₂₀-arylalkyl radical,

reacting the resulting high-reactivity isobutene homo- or copolymerwhich has a content of at least 50 mol % of terminal vinylidene doublebonds per polyisobutene chain end with at least n equivalents of acompound which introduces the low molecular weight polar A group or asubstructure of the low molecular weight polar A group and, in the caseof reaction with a substructure, completing the formation of the lowmolecular weight polar A group by further reactions.

The polymerization method for isobutene or isobutene-comprising monomermixtures according to embodiment (A), which is essential to thisinvention, is described in essence in the above-cited European patentapplication with reference number 10157068.7, which was yet to bepublished at the priority date of the present application, and isreproduced below.

Isobutene homopolymers are understood in the context of the presentinvention to mean those polymers which, based on the polymer, are formedfrom isobutene to an extent of at least 98 mol %, preferably to anextent of at least 99 mol %. Accordingly, isobutene copolymers areunderstood to mean those polymers which comprise more than 2 mol % ofcopolymerized monomers other than isobutene, for example linear butenes.

In the context of the present invention, the following definitions applyto generically defined radicals:

A C₁- to C₈-alkyl radical is a linear or branched alkyl radical having 1to 8 carbon atoms. Examples thereof are methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl-propyl,1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl andthe constitutional isomers thereof, such as 2-ethylhexyl. Such C₁- toC₈-alkyl radicals may to a small extent also comprise heteroatoms suchas oxygen, nitrogen or halogen atoms, for example chlorine, and/oraprotic functional groups, for example carboxyl ester groups, cyanogroups or nitro groups.

A C₁- to C₂₀-alkyl radical is a linear or branched alkyl radical having1 to 20 carbon atoms. Examples thereof are the abovementioned C₁- toC₈-alkyl radicals, and additionally n-nonyl, isononyl, n-decyl,2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl,n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C₁- toC₂₀-alkyl radicals may to a small extent also comprise heteroatoms suchas oxygen, nitrogen or halogen atoms, for example chlorine, and/oraprotic functional groups, for example carboxyl ester groups, cyanogroups or nitro groups.

A C₅- to C₈-cycloalkyl radical is a saturated cyclic radical which maycomprise alkyl side chains. Examples thereof are cyclopentyl, 2- or3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl,2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl,cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C₅- to C₈-cycloalkylradicals may to a small extent also comprise heteroatoms such as oxygen,nitrogen or halogen atoms, for example chlorine, and/or aproticfunctional groups, for example carboxyl ester groups, cyano groups ornitro groups.

A C₆- to C₂₀-aryl radical or a C₆- to C₁₂-aryl radical is preferablyoptionally substituted phenyl, optionally substituted naphthyl,optionally substituted anthracenyl or optionally substitutedphenanthrenyl. Such aryl radicals may be a 1 to 5 aprotic substituentsor aprotic functional groups, for example C₁- to C₈-alkyl, C₁- toC₈-haloalkyl such as C₁- to C₈-chloroalkyl or C₁- to C₈-fluoroalkyl,halogens such as chlorine or fluorine, nitro, cyano or phenyl. Examplesof such aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl,pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl,bis(tri-fluoromethyl)phenyl, (trichloro)methylphenyl andbis(trichloromethyl)phenyl.

A C₇- to C₂₀-arylalkyl radical or a C₇- to C₁₂-arylalkyl radical ispreferably optionally substituted C₁- to C₄-alkylphenyl such as benzyl,o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropylor 1-, 2-, 3- or 4-phenylbutyl, optionally substituted C₁- toC₄-alkylnaphthyl such as naphthylmethyl, optionally substituted C₁- toC₄-alkylanthracenyl such as anthracenylmethyl, or optionally substitutedC₁- to C₄-alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkylradicals may bear 1 to 5 aprotic substituents or aprotic functionalgroups, especially on the aryl moiety, for example C₁- to C₈-alkyl, C₁-to C₈-haloalkyl such as C₁- to C₈-chloroalkyl or C₁- to C₈-fluoroalkyl,halogen such as chlorine or fluorine, nitro or phenyl.

Suitable iron halides in the corresponding complexes with donors are,for example, iron(II) fluoride, iron(III) fluoride, iron(II) chloride,iron(III) chloride, iron(II) bromide and iron(III) bromide, and mixturesthereof. Preference is given to using iron chloride, i.e. iron(II)chloride and iron(III) chloride, and mixtures of iron(II) chloride andiron(III) chloride, but especially iron(III) chloride alone. It is alsopossible to use iron halides, especially iron chlorides, which have beenobtained from iron-comprising metal alloys, i.e. in addition to ironhalides, especially iron chlorides, also comprise other metal halides,though the iron halides, especially iron chlorides, preferablyconstitute the main constituents of such mixtures.

A suitable aluminum trihalide is especially aluminum trifluoride,aluminum trichloride or aluminum tribromide. A useful alkylaluminumhalide is especially a mono(C₁- to C₄-alkyl)aluminum dihalide or adi(C₁- to C₄-alkyl)aluminum monohalide, for example methylaluminumdichloride, ethylaluminum dichloride, dimethylaluminum chloride ordiethylaluminum chloride. In a preferred embodiment, isobutene or anisobutene-comprising monomer mixture is polymerized in the presence ofan aluminum trichloride-donor complex effective as a polymerizationcatalyst.

If the iron halide-donor complex, aluminum trihalide-donor complex oralkylaluminum halide-donor complex effective as a polymerizationcatalyst comprises, as the donor, an organic compound with at least oneether function, compounds with at least one ether function are alsounderstood to mean acetals and hemiacetals.

In a preferred embodiment of the present invention, an iron halide-donorcomplex, an aluminum trihalide-donor complex or an alkylaluminumhalide-donor complex, especially an iron chloride-donor complex or analuminum trichloride-donor complex, is used, which comprises, as thedonor, a dihydrocarbyl ether of the general formula R¹—O—R² in which thevariables R¹ and R² are each independently C₁- to C₂₀-alkyl radicals,especially C₁- to C₈ alkyl radicals, C₅- to C₈-cycloalkyl radicals, C₆-to C₂₀-aryl radicals, especially C₆- to C₁₂ aryl radicals, or C₇- toC₂₀-arylalkyl radicals, especially C₇- to C₁₂-arylalkyl radicals.

The dihydrocarbyl ethers mentioned may be open-chain or cyclic, wherethe two variables R¹ and R² in the case of the cyclic ethers may join toform a ring, where such rings may also comprise two or three etheroxygen atoms. Examples of such open-chain and cyclic dihydrocarbylethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropylether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether,di-n-pentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octylether, di-(2-ethylhexyl)ether, methyl n-butyl ether, methyl sec-butylether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n-butylether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl-n-butylether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyltert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether,isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexylether, methyl n-octyl ether, methyl 2-ethylhexyl ether, ethyl n-hexylether, ethyl n-octyl ether, ethyl 2-ethylhexyl ether, n-butyl n-octylether, n-butyl 2-ethylhexyl ether, tetrahydrofuran, tetrahydropyran,1,2-, 1,3- and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, ditolylether, dixylyl ether and dibenzyl ether. Among the dihydrocarbyl ethersmentioned, di-n-butyl ether and diphenyl ether have been found to beparticularly advantageous as donors for the iron halide-donor complexes,the aluminum trihalide-donor complexes or the alkylaluminum halide-donorcomplexes, especially the iron chloride-donor complexes or the aluminumtrichloride-donor complexes.

In a further preferred embodiment of the present invention, as analternative, an iron halide-donor complex, an aluminum trihalide-donorcomplex or an alkylaluminum halide-donor complex, especially an ironchloride-donor complex or an aluminum trichloride-donor complex, isused, which comprises, as the donor, a hydrocarbyl carboxylate of thegeneral formula R³—COOR⁴ in which the variables R³ and R⁴ are eachindependently C₁- to C₂₀-alkyl radicals, especially C₁- to C₈ alkylradicals, C₅- to C₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals,especially C₆- to C₁₂ aryl radicals, or C₇- to C₂₀-arylalkyl radicals,especially C₇- to C₁₂-arylalkyl radicals.

Examples of the hydrocarbyl carboxylates mentioned are methyl formate,ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate,sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate,ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate,sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methylpropionate, ethyl propionate, n-propyl propionate, isopropyl propionate,n-butyl propionate, sec-butyl propionate, isobutyl propionate,tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propylbutyrate, isopropyl butyrate, n-butyl butyrate, sec-butyl butyrate,isobutyl butyrate, tert-butyl butyrate, methyl cyclohexanecarboxylate,ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropylcyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butylcyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propylbenzoate, isopropyl benzoate, n-butyl benzoate, sec-butyl benzoate,isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, ethylphenylacetate, n-propyl phenylacetate, isopropyl phenylacetate, n-butylphenylacetate, sec-butyl phenylacetate, isobutyl phenylacetate andtert-butyl phenylacetate. Among the hydrocarbyl carboxylates mentioned,ethyl acetate has been found to be particularly advantageous as a donorfor the iron halide-donor complexes, the aluminum trihalide-donorcomplexes or the alkylaluminum halide complexes, especially the aluminumtrichloride-donor complexes.

In addition, particularly advantageous dihydrocarbyl ethers andhydrocarbyl carboxylates as donors for the iron halide-donor complexes,the aluminum trihalide-donor complexes or the alkylaluminum halide-donorcomplexes, especially the iron chloride-donor complexes or the aluminumtrichloride-donor complexes, have been found to be those in which thedonor compound has a total carbon number of 3 to 16, preferably of 4 to16, especially of 4 to 12, in particular of 4 to 8. In the specific caseof the dihydrocarbyl ethers, preference is given in particular to thosehaving a total of 6 to 14 and especially 8 to 12 carbon atoms. In thespecific case of the hydrocarbyl carboxylates, preference is given inparticular to those having a total of 3 to 10 and especially 4 to 6carbon atoms.

The molar ratio of the donor compounds mentioned to the iron halide, tothe aluminum trihalide or to the alkylaluminum halide, especially to theiron chloride or to the aluminum trichloride, in the donor complexgenerally varies within the range from 0.3:1 to 1.5:1, especially from0.5:1 to 1.2:1, in particular 0.7:1 to 1.1:1; in most cases it is 1:1.However, it is also possible to work with a greater excess of the donorcompounds, often up to a 10-fold and especially 3-fold molar excess; theexcess amount of donor compounds then acts additionally as a solvent ordiluent.

Typically, the iron halide-donor complex, the aluminum trihalide-donorcomplex or the alkylaluminum halide-donor complex, especially the ironchloride-donor complex or the aluminum trichloride-donor complex, isprepared separately prior to the polymerization from the iron halide,the aluminum trihalide or the alkylaluminum halide, especially fromanhydrous iron chloride or aluminum trichloride, and the donor compound,and is then—usually dissolved in an inert solvent such as a halogenatedhydrocarbon, for example dichloromethane—added to the polymerizationmedium. However, the complex can also be prepared in situ prior to thepolymerization.

In a preferred embodiment of the present invention, the polymerizationis performed with additional use of a mono- or polyfunctional,especially mono-, di- or trifunctional, initiator which is selected fromorganic hydroxyl compounds, organic halogen compounds, protic acids andwater. It is also possible to use mixtures of the initiators mentioned,for example mixtures of two or more organic hydroxyl compounds, mixturesof two or more organic halogen compounds, mixtures of one or moreorganic hydroxyl compounds and one or more organic halogen compounds,mixtures of one or more organic hydroxyl compounds and water, mixturesof one or more organic halogen compounds and water or mixtures of one ormore protic acids and water. The initiator may be mono-, di- orpolyfunctional, i.e. one, two or more hydroxyl groups or halogen atoms,which start the polymerization reaction, may be present in the initiatormolecule. In the case of di- or polyfunctional initiators, telechelicisobutene polymers with two or more, especially two or three,polyisobutene chain ends are typically obtained.

Organic hydroxyl compounds which have only one hydroxyl group in themolecule and are suitable as monofunctional initiators includeespecially alcohols and phenols, in particular those of the generalformula R⁵—OH, in which R⁵ denotes C₁- to C₂₀-alkyl radicals, especiallyC₁- to C₈-alkyl radicals, C₅- to C₈-cycloalkyl radicals, C₆- to C₂₀-arylradicals, especially C₆- to C₁₂-aryl radicals, or C₇- to C₂₀-arylalkylradicals, especially C₇- to C₁₂-arylalkyl radicals. In addition, the R⁵radicals may also comprise mixtures of the abovementioned structuresand/or have other functional groups than those already mentioned, forexample a keto function, a nitroxide or a carboxyl group, and/orheterocyclic structural elements.

Typical examples of such organic monohydroxyl compounds are methanol,ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol,tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol,2-ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- andp-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and2-phenylethanol, 1- and 2-(p-methoxyphenyl)ethanol, 1-, 2- and3-phenyl-1-propanol, 1-, 2- and 3-(p-methoxyphenyl)-1-propanol, 1- and2-phenyl-2-propanol, 1- and 2-(p-methoxyphenyl)-2-propanol, 1-, 2-, 3-and 4-phenyl-1-butanol, 1-, 2-, 3- and 4-(p-methoxyphenyl)-1-butanol,1-, 2-, 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and4-(p-methoxyphenyl)-2-butanol, 9-methyl-9H-fluoren-9-ol,1,1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol,4-(1-hydroxy-1-phenylethyl)benzonitrile, cyclopropyldiphenylmethanol,1-hydroxy-1,1-diphenylpropan-2-one, benzilic acid, 9-phenyl-9-fluorenol,triphenylmethanol, diphenyl(4-pyridinyl)methanol,alpha,alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol(especially polymer-bound as a solid phase),alpha-tert-butyl-4-chloro-4′-methylbenzhydrol,cyclohexyldiphenylmethanol, alpha-(p-tolyl)-benzhydrol,1,1,2-triphenylethanol, alpha,alpha-diphenyl-2-pyridineethanol,alpha,alpha-4-pyridylbenzhydrol N-oxide, 2-fluorotriphenylmethanol,triphenylpropargyl alcohol, 4-[(diphenyl)hydroxy-methypenzonitrile,1-(2,6-dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol,1,1,2-triphenylpropan-1-ol and p-anisaldehyde carbinol.

Organic hydroxyl compounds which have two hydroxyl groups in themolecule and are suitable as bifunctional initiators are especiallydihydric alcohols or diols having a total carbon number of 2 to 30,especially of 3 to 24, in particular of 4 to 20, and bisphenols having atotal carbon number of 6 to 30, especially of 8 to 24, in particular of10 to 20, for example ethylene glycol, 1,2- and 1,3-propylene glycol,1,4-butylene glycol, 1,6-hexylene glycol, 1,2-, 1,3- or1,4-bis(1-hydroxy-1-methylethyl)benzene (o-, m- or p-dicumyl alcohol),bisphenol A, 9,10-di-hydro-9,10-dimethyl-9,10-anthracenediol,1,1-diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and9-[2-(hydroxymethyl)phenyl]-9-fluorenol.

Organic halogen compounds which have one halogen atom in the moleculeand are suitable as monofunctional initiators are in particularcompounds of the general formula R⁶-Hal in which Hal is a halogen atomselected from fluorine, iodine and especially chlorine and bromine, andR⁶ denotes C₁- to C₂₀-alkyl radicals, especially C₁- to C₈-alkylradicals, C₅- to C₈-cycloalkyl radicals or C₇- to C₂₀-arylalkylradicals, especially C₇- to C₁₂-arylalkyl radicals. In addition, the R⁶radicals may also comprise mixtures of the abovementioned structuresand/or have other functional groups than those already mentioned, forexample a keto function, a nitroxide or a carboxyl group, and/orheterocyclic structural elements.

Typical examples of such monohalogen compounds are methyl chloride,methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane,1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane,1-bromobutane, sec-butyl chloride, sec-butyl bromide, isobutyl chloride,isobutyl bromide, tert-butyl chloride, tert-butyl bromide,1-chioropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane,1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromooctane,1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride,cyclohexyl bromide, benzyl chloride, benzyl bromide,1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane,1-phenyl-2-chloroethane, 1-phenyl-2-bromoethane,1-phenyl-1-chloropropane, 1-phenyl-1-bromopropane,1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane,2-phenyl-2-chloropropane, 2-phenyl-2-bromopropane,1-phenyl-3-chloropropane, 1-phenyl-3-bromopropane,1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane,1-phenyl-2-chlorobutane, 1-phenyl-2-bromobutane,1-phenyl-3-chlorobutane, 1-phenyl-3-bromobutane,1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane,2-phenyl-1-chlorobutane, 2-phenyl-1-bromobutane,2-phenyl-2-chlorobutane, 2-phenyl-2-bromobutane,2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutaneand 2-phenyl-4-bromobutane.

Organic halogen compounds which have two halogen atoms in the moleculeand are suitable as difunctional initiators are, for example,1,3-bis(1-bromo-1-methylethyl)benzene, 1,3-bis(2-chloro-2-propyl)benzene(1,3-dicumyl chloride) and 1,4-bis(2-chloro-2-propyl)benzene(1,4-dicumyl chloride).

The initiator is more preferably selected from organic hydroxylcompounds in which one or more hydroxyl groups are each bonded to ansp³-hybridized carbon atom (“alcohols”) or to an aromatic ring(“phenols”), organic halogen compounds, in which one or more halogenatoms are each bonded to an sp³-hybridized carbon atom, protic acids andwater. Among these, preference is given in particular to an initiatorselected from organic hydroxyl compounds in which one or more hydroxylgroups are each bonded to an sp³-hybridized carbon atom.

In the case of the organic halogen compounds as initiators, particularpreference is further given to those in which the one or more halogenatoms are each bonded to a secondary or especially to a tertiarysp³-hybridized carbon atom.

Preference is given in particular to initiators which bear, on such ansp³-hydridized carbon atom, in addition to the hydroxyl group, the R¹⁰,R¹¹ and R¹² radicals, which are each independently hydrogen, C₁- toC₂₀-alkyl, C₅- to C₈-cycloalkyl, C₆- to C₂₀-aryl, C₇- to C₂₀-alkylarylor phenyl, where any aromatic ring may also bear one or more, preferablyone two, C₁- to C₄-alkyl, C₁- to C₄-alkoxy, C₁- to C₄-hydroxyalkyl orC₁- to C₄-haloalkyl radicals as substituents, where not more than one ofthe variables R¹⁰, R¹¹ and R¹² is hydrogen and at least one of thevariables R¹⁰, R¹¹ and R¹² is phenyl which may also bear one or more,preferably one or two, C₁- to C₄-alkyl, C₁- to C₄-alkoxy, C₁- toC₄-hydroxyalkyl or C₁- to C₄-haloalkyl radicals as substituents.

Examples of useful protic acids include hydrochloric acid, hydrobromicacid, hydrofluoric acid, sulfuric acid, hydrocyanic acid and mixturesthereof. However, the protic acids used may also be protonated ethers.

For the present invention, very particular preference is given toinitiators selected from water, one or more protic acids, methanol,ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol, n-propanol,isopropanol, 2-phenyl-2-propanol(cumene), n-butanol, isobutanol,sec-butanol, tert-butanol, 1-phenyl-1-chloroethane,2-phenyl-2-chloropropane(cumyl chloride), tert-butyl chloride and 1,3-or 1,4-bis(1-hydroxy-1-methylethyl)benzene and mixtures thereof. Amongthese, preference is given in particular to initiators selected fromwater, one or more protic acids, methanol, ethanol, 1-phenylethanol,1-(p-methoxy-phenyl)ethanol, n-propanol, isopropanol,2-phenyl-2-propanol(cumene), n-butanol, isobutanol, sec-butanol,tert-butanol,1-phenyl-1-chloroethane and 1,3- or1,4-bis(1-hydroxy-1-methylethyl)benzene and mixtures thereof.

The molar ratio of the initiators mentioned to the isobutene monomerused in the case of homopolymerization of isobutene, or to the totalamount of the polymerizable monomers used in the case ofcopolymerization of isobutene, based on each individual functional siteof the initiator, according to embodiment (A) is generally 0.0005: 1 to0.1:1, especially 0.001:1 to 0.075: 1, in particular 0.0025: 1 to0.05: 1. When water is used as the sole initiator or in combination withorganic hydroxyl compounds and/or organic halogen compounds as furtherinitiators, the molar ratio of water to the isobutene monomer used inthe case of homopolymerization of isobutene, or to the total amount ofthe polymerizable monomers used in the case of copolymerization ofisobutene is especially 0.0001:1 to 0.1:1, in particular 0.0002: 1 to0.05:1.

A proportion of the initiator molecules added as organic hydroxyl orhalogen compounds is incorporated into the polymer chains in embodiment(A). The proportion (I_(eff)) of polymer chains which are started bysuch an incorporated organic initiator molecule may be up to 100%, andis generally 5 to 90%. The remaining polymer chains arise either fromwater originating from traces of moisture as an initiator molecule, orfrom chain transfer reactions.

In a further preferred embodiment of the present invention, thepolymerization is performed in the presence of 0.01 to 10 mmol,especially of 0.05 to 5.0 mmol, in particular of 0.1 to 1.0 mmol, basedin each case on 1 mol of isobutene monomer used in the case ofhomopolymerization of isobutene, or on 1 mol of the total amount of thepolymerizable monomers used in the case of copolymerization ofisobutene, of a basic nitrogen compound.

Such a basic nitrogen compound used may be an aliphatic, cycloaliphaticor aromatic amine of the general formula R⁷—NR⁸R⁹, or else ammonia, inwhich the variables R⁷, R⁸ and R⁹ are each independently hydrogen, C₁-to C₂₀-alkyl radicals, especially C₁- to C₈-alkyl radicals, C₅- toC₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals, especially C₆- toC₁₂-aryl radicals, or C₇- to C₂₀-arylalkyl radicals, especially C₇- toC₁₂-arylalkyl radicals. When none of these variables is hydrogen, theamine is a tertiary amine. When one of these variables is hydrogen, theamine is a secondary amine. When two of these variables is hydrogen, theamine is a primary amine. When all these variables are hydrogen, theamine is ammonia.

Typical examples of such amines of the general formula R⁷—NR⁸R⁹ aremethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine,n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine,cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine,di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine,di-sec-butylamine, diisobutylamine, di-tert-amylamine, di-n-hexylamine,di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine,dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine,triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine,tri-tert-butylamine, tri-sec-butylamine, tri-isobutylamine,tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine,tri-n-octylamine, tri-(2-ethylhexyl)amine, tricyclopentylamine,tricyclohexylamine, triphenylamine, dimethylethylamine,methyl-n-butylamine, N-methyl-N-phenylamine, N,N-dimethyl-N-phenylamine,N-methyl-N,N-diphenylamine or N-methyl-N-ethyl-N-n-butylamine.

In addition, such a basic nitrogen compound used may also be a compoundhaving a plurality of, especially having two or three, nitrogen atomsand having 2 to 20 carbon atoms, where these nitrogens may eachindependently bear hydrogen atoms or aliphatic, cycloaliphatic oraromatic substituents. Examples of such polyamines are1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine,diethylenetriamine, N-methyl-1,2-ethylenediamine,N,N-dimethyl-1,2-ethylenediamine, N,N′-dimethyl-1,2-ethylenediamine orN,N-dimethyl-1,3-propylenediamine.

However, a suitable basic nitrogen compound of this kind is especially asaturated, partly unsaturated or unsaturated nitrogen-containingfive-membered or six-membered heterocyclic ring which comprises one, twoor three ring nitrogen atoms and may have one or two further ringheteroatoms from the group of oxygen and sulfur and/or hydrocarbylradicals, especially C₁- to C₄-alkyl radicals and/or phenyl, and/orfunctional groups or heteroatoms as substituents, especially fluorine,chlorine, bromine, nitro and/or cyano, for example pyrrolidine, pyrrole,imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine,pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or1,2,5-triazine, 1,2,5-oxathiazine, 2H-1,3,5-thiadiazine or morpholine.

However, a very particularly suitable basic nitrogen compound of thiskind is pyridine or a derivative of pyridine (especially a mono-, di- ortri-C₁- to C₄-alkyl-substituted pyridine) such as 2-, 3-, or4-methylpyridine (picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine (collidine),2-, 3,- or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-,2,5-, 2,6- or 3,5-di-tert-butylpyridine or else 2-, 3,- or4-phenylpyridine.

It is possible to use a single basic nitrogen compound or mixtures ofsuch basic nitrogen compounds.

The polymerization methods essential to the invention, which has beenspecified for the present invention, for isobutene orisobutene-comprising monomer mixtures according to embodiment (B) isdescribed hereinafter.

Isobutene homopolymers are understood in the context of the presentinvention to mean those polymers which, based on the polymer, are formedfrom isobutene to an extent of at least 98 mol %, preferably to anextent of at least 99 mol %. Accordingly, isobutene copolymers areunderstood to mean those polymers which comprise more than 2 mol % ofcopolymerized monomers other than isobutene, for example linear butenes.

In the context of the present invention, the following definitions applyto generically defined radicals:

A C₁- to C₈-alkyl radical is a linear or branched alkyl radical having 1to 8 carbon atoms. Examples thereof are methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl-propyl,1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl andthe constitutional isomers thereof, such as 2-ethylhexyl. Such C₁- toC₈-alkyl radicals may to a small extent also comprise heteroatoms suchas oxygen, nitrogen or halogen atoms, e.g. chlorine or fluorine, and/oraprotic functional groups, for example carboxyl ester groups, cyanogroups or nitro groups.

A C₁- to C₂₀-alkyl radical is a linear or branched alkyl radical having1 to 20 carbon atoms. Examples thereof are the abovementioned C₁- toC₈-alkyl radicals, and additionally n-nonyl, isononyl, n-decyl,2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl,n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Such C₁- toC₂₀-alkyl radicals may to a small extent also comprise heteroatoms suchas oxygen, nitrogen or halogen atoms, e.g. chlorine or fluorine, and/oraprotic functional groups, for example carboxyl ester groups, cyanogroups or nitro groups.

A C1- to C₂₀-haloalkyl radical or a C₁- to C₈-haloalkyl radical is aradical with the base skeletons specified above for C₁- to C₂₀-alkylradicals or C₁- to C₈-alkyl radicals, but in which the hydrogen atomshave been replaced to a relatively high degree by halogen atoms,especially by fluorine and/or chlorine atoms. Preferably all orvirtually all hydrogen atoms have been replaced by halogen atoms,especially by fluorine and/or chlorine atoms. Typical examples of suchradicals are C₁- to C₄-alkyl radicals in which at least 60%, especiallyat least 75%, in particular at least 90%, of the number of the hydrogenatoms have been replaced by fluorine and/or chlorine atoms, for exampledichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl,chlorodifluoromethyl, fluorodichloromethyl, pentachloroethyl orpentafluoroethyl.

A C₅- to C₈-cycloalkyl radical is a saturated cyclic radical which maycomprise alkyl side chains. Examples thereof are cyclopentyl, 2- or3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl,2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl,cyclooctyl, 2-, 3-, 4- or 5-methylcyclooctyl. Such C₅- to C₈-cycloalkylradicals may to a small extent also comprise heteroatoms such as oxygen,nitrogen or halogen atoms, e.g. chlorine or fluorine, and/or aproticfunctional groups, for example carboxyl ester groups, cyano groups ornitro groups.

A C₆- to C₂₀-aryl radical or a C₆- to C₁₂-aryl radical is preferablyoptionally substituted phenyl, optionally substituted naphthyl,optionally substituted anthracenyl or optionally substitutedphenanthrenyl. Such aryl radicals may be a 1 to 5 aprotic substituentsor aprotic functional groups, for example C₁- to C₈-alkyl, C₁- toC₈-haloalkyl such as C₁- to C₈-chloroalkyl or C₁- to C₈-fluoroalkyl,halogens such as chlorine or fluorine, nitro, cyano or phenyl. Examplesof such aryl radicals are phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, tolyl, nitrophenyl, chlorophenyl, dichlorophenyl,pentafluorophenyl, pentachlorophenyl, (trifluoromethyl)phenyl,bis(tri-fluoromethyl)phenyl, (trichloro)methylphenyl andbis(trichloromethyl)phenyl.

A C₇- to C₂₀-arylalkyl radical or a C₇- to C₁₂-arylalkyl radical ispreferably optionally substituted C₁- to C₄-alkylphenyl such as benzyl,o-, m- or p-methylbenzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropylor 1-, 2-, 3- or 4-phenylbutyl, optionally substituted C₁- toC₄-alkylnaphthyl such as naphthylmethyl, optionally substituted C₁- toC₄-alkylanthracenyl such as anthracenylmethyl, or optionally substitutedC₁- to C₄-alkylphenanthrenyl such as phenanthrenylmethyl. Such arylalkylradicals may bear 1 to 5 aprotic substituents or aprotic functionalgroups, especially on the aryl moiety, for example C₁- to C₈-alkyl, C₁-to C₈-haloalkyl such as to C₈-chloroalkyl or C₁- to C₈-fluoroalkyl,halogen such as chlorine or fluorine, nitro or phenyl.

The process according to the invention for preparation ofhigh-reactivity isobutene homo- or copolymers generally proceeds—causedby the use of the complex which is effective as a polymerizationcatalyst and is formed from at least one Lewis acid and optionally atleast one donor and the initiators described—by a cationic reactionmechanism.

The feature essential to the invention is the use of an organic sulfonicacid of the general formula Z—SO₃H as at least one initiator in thepolymerization process according to the invention. It will beappreciated that it is also possible to use mixtures of differentsulfonic acids Z—SO₃H. In addition to these sulfonic acid initiators, itis also possible to use further initiator molecules from other chemicalsubstance classes.

The variable Z preferably represents a C₁- to C₈-alkyl radical, C₁- toC₈-haloalkyl radical, C₅- to C₈-cycloalkyl radical, C₆- to C₁₂-arylradical or a C₇- to C₁₂-arylalkyl radical. Z more preferably representsa C₁- to C₄-alkyl radical, a C₁- to C₄-haloalkyl radical, an optionallysubstituted phenyl radical, e.g. a tolyl radical or a xylyl radical, oran optionally substituted C₁- to C₄-alkylphenyl radical, e.g. a benzylradical.

In a particularly preferred embodiment of the present invention, the atleast one initiator used is an organic sulfonic acid selected frommethanesulfonic acid, trifluoromethane-sulfonic acid,trichloromethanesulfonic acid and toluenesulfonic acid, or mixturesthereof.

Suitable Lewis acids as a polymerization catalyst or in the complexeffective as a polymerization catalyst are in principle all inorganicmolecules identified as Lewis acids by definition, but especiallyhalogen compounds of metals and semimetals of the Periodic Table of theElements whose valences are fully satisfied by halogen atoms or which,in addition to the halogen substituents, also bear one or more organiccarbon radicals—especially C₁- to C₄-alkyl radicals. Useful halogensubstituents in these element halides and alkyl element halides hereinclude iodine, bromine and especially fluorine and in particularchlorine. It is of course also possible to use mixtures of those elementhalides or of those alkyl element halides with one another in each caseand also with each other.

If, for example, the halides or alkyl halides of aluminum are used assuch Lewis acids, the following species can typically be used: aluminumtrifluoride, aluminum trichloride, aluminum tribromide; as alkylaluminumhalides, mono(C₁- to C₄-alkyl)aluminum dihalides or di(C₁- toC₄-alkyl)aluminum monohalide such as methylaluminum dichloride,ethylaluminum dichloride, dimethylaluminum chloride or diethylaluminumchloride.

In a preferred embodiment, the Lewis acid used for the polymerizationcatalyst or the complex effective as a polymerization catalyst is atleast one compound selected from the binary chlorine and fluorinecompounds of the elements of transition groups 1 to 8 and of main groups3 to 5 of the Periodic Table, and the binary chlorine compounds may bepreferable over the binary fluorine compounds of these elements.

Typical binary chlorine compounds of this kind are ScCl₃, YCl₃, YbCl₃,TiCl₃, TiCl₄, ZrCl₄, HfCl₄, VCl₃, VCl₄, NbCl₃, NbCl₅, TaCl₅, CrCl₂,CrCl₃, MoCl₃, MoCl₅, WCl₅, WCl₆, MnCl₂, ReCl₃, ReCl₅, FeCl₂, FeCl₃,RuCl₃, OsCl₃, CoCl₂, CoCl₃, RhCl₃, IrCl₃, NiCl₂, PdCl₂, PtCl₂, CuCl,CuCl₂, AgCl, AuCl, ZnCl₂, CdCl₂, HgCl, HgCl₂, BCl₃, AlCl₃, GaCl₃, InCl₃,TlCl₃, SiCl₄, GeCl₄, SnCl₂, SnCl₃, SnCl₄, PbCl₂, PbCl₄, PCl₃, PCl₅,AsCl₃, SbCl₃, SbCl₅ and BiCl₃. Particular preference among these isgiven to BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃ and ZnCl₂.

Typical binary fluorine compounds of this kind are ScF₃, YF₃, YbF₃,TiF₃, TiF₄, ZrF₄, HfF₄, VF₃, VF₄, NbF₃, NbF₅, TaF₅, CrF₂, CrF₃, MoF₃,MoF₅, WF₅, WF₆, MnF₂, ReF₃, ReF₅, FeF₂, FeF₃, RuF₃, OsF₃, CoF₂, CoF₃,RhF₃, IrF₃, NiF₂, PdF₂, PtF₂, CuF, CuF₂, AgF, AuF, ZnF₂, CdF₂, HgF,HgF₂, BF₃, AlF₃, GaF₃, InF₃, TlF₃, SiF₄, GeF₄, SnF₂, SnF₃, SnF₄, PbF₂,PbF₄, PF₃, PF₅, AsF₃, SbF₃, SbF₅ and BiF₃. Among these, particularpreference is given to BF₃, AlF₃, TiF₄, FeF₂, FeF₃ and ZnF₂. It is alsopossible to use mixtures of binary chlorine and fluorine compounds.

It is often also possible to use binary bromine compounds as Lewis acidsof this kind; such bromine compounds are, for example: TiBr₃, TiBr₄,ZrBr₄, VBr₃, VBr₄, CrBr₂, CrBr₃, MoBr₃, MoBr₅, WBr₅, WBr₆, MnBr₂, FeBr₂,FeBr₃, CoBr₂, CoBr₃, NiBr₂, PdBr₂, PtBr₂, CuBr, CuBr₂, AgBr, AuBr,ZnBr₂, CdBr₂, HgBr, HgBr₂, BBr₃, AlBr₃, SiBr₄, SnBr₂, SnBr₃, SnBr₄,PbBr₂, PbBr₄, PBr₃, PBr₅, AsBr₃, SbBr₃, SbBr₅ and BiBr₃.

Very particular preference is given to using the preferred sulfonic acidinitiators methanesulfonic acid, trifluoromethanesulfonic acid,trichloromethanesulfonic acid and toluenesulfonic acid together with thepreferred Lewis acids or Lewis acid complexes with BCl₃, AlCl₃, TiCl₄,FeCl₂, FeCl₃, ZnCl₂, BF₃, AlF₃, TiF₄, FeF₂, FeF₃ and/or ZnF₂, inparticular methanesulfonic acid together with AlCl₃, BF₃ or FeCl₃,especially when Lewis acid complexes which comprise the dihydrocarbylethers of the general formula R¹—O—R² and/or hydrocarbyl carboxylates ofthe general formula R³—COOR⁴ specified below as preferred as donors areused.

In the process according to the invention, preference is given to usinga complex which is effective as a polymerization catalyst and comprises,as the donor, an organic compound with at least one ether function or acarboxylic ester function. It is of course also possible to use mixturesof different organic compounds with at least one ether function and/orof different organic compounds with at least one carboxylic esterfunction. If the complex effective as a polymerization catalystcomprises, as the donor, an organic compound with at least one etherfunction, compounds with at least one ether function are also understoodto mean acetals and hemiacetals.

In a preferred embodiment of the present invention, a complex which iseffective as a polymerization catalyst and is formed from at least oneLewis acid and at least one donor is used, in which the organic compoundwhich functions as the donor is a dihydrocarbyl ether of the generalformula R¹—O—R² in which the variables R¹ and R² are each independentlyC₁- to C₂₀-alkyl radicals, especially C₁- to C₈ alkyl radicals, C₅- toC₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals, especially C₆- to C₁₂aryl radicals, or C₇- to C₂₀-arylalkyl radicals, especially C₇- toC₁₂-arylalkyl radicals, or a hydrocarbyl carboxylate of the generalformula R³—COOR⁴ in which the variables R³ and R⁴ are each independentlyC₁- to C₂₀-alkyl radicals, especially C₁- to C₈ alkyl radicals, C₅- toC₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals, especially C₆- to C₁₂aryl radicals, or C₇- to C₂₀-arylalkyl radicals, especially C₇- toC₁₂-arylalkyl radicals.

The dihydrocarbyl ethers mentioned may be open-chain or cyclic, wherethe two variables R¹ and R² in the case of the cyclic ethers may join toform a ring, where such rings may also comprise two or three etheroxygen atoms. Examples of such open-chain and cyclic dihydrocarbylethers are dimethyl ether, diethyl ether, di-n-propyl ether, diisopropylether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether,di-n-pentyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octylether, di-(2-ethylhexyl)ether, methyl n-butyl ether, methyl sec-butylether, methyl isobutyl ether, methyl tert-butyl ether, ethyl n-butylether, ethyl sec-butyl ether, ethyl isobutyl ether, n-propyl-n-butylether, n-propyl sec-butyl ether, n-propyl isobutyl ether, n-propyltert-butyl ether, isopropyl n-butyl ether, isopropyl sec-butyl ether,isopropyl isobutyl ether, isopropyl tert-butyl ether, methyl n-hexylether, methyl n-octyl ether, methyl 2-ethylhexyl ether, ethyl n-hexylether, ethyl n-octyl ether, ethyl 2-ethylhexyl ether, n-butyl n-octylether, n-butyl 2-ethylhexyl ether, tetrahydrofuran, tetrahydropyran,1,2-, 1,3- and 1,4-dioxane, dicyclohexyl ether, diphenyl ether, ditolylether, dixylyl ether and dibenzyl ether. Among the dihydrocarbyl ethersmentioned, di-n-butyl ether and diphenyl ether have been found to beparticularly advantageous here as donors, especially in combination withthe Lewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃ and ZnCl₂.

Examples of the hydrocarbyl carboxylates mentioned are methyl formate,ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate,sec-butyl formate, isobutyl formate, tert-butyl formate, methyl acetate,ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate,sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methylpropionate, ethyl propionate, n-propyl propionate, isopropyl propionate,n-butyl propionate, sec-butyl propionate, isobutyl propionate,tert-butyl propionate, methyl butyrate, ethyl butyrate, n-propylbutyrate, isopropyl butyrate, n-butyl butyrate, sec-butyl butyrate,isobutyl butyrate, tert-butyl butyrate, methyl cyclohexanecarboxylate,ethyl cyclohexanecarboxylate, n-propyl cyclohexanecarboxylate, isopropylcyclohexanecarboxylate, n-butyl cyclohexanecarboxylate, sec-butylcyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, tert-butylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, n-propylbenzoate, isopropyl benzoate, n-butyl benzoate, sec-butyl benzoate,isobutyl benzoate, tert-butyl benzoate, methyl phenylacetate, ethylphenylacetate, n-propyl phenylacetate, isopropyl phenylacetate, n-butylphenylacetate, sec-butyl phenylacetate, isobutyl phenylacetate andtert-butyl phenylacetate. Among the hydrocarbyl carboxylates mentioned,ethyl acetate has been found to be particularly advantageous here as adonor, especially in combination with the Lewis acids BCl₃, AlCl₃,TiCl₄, FeCl₂, FeCl₃ and ZnCl₂.

In addition, particularly advantageous dihydrocarbyl ethers andhydrocarbyl carboxylates as donors, especially in combination with theLewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂, FeCl₃ and ZnCl₂, have been foundto be those in which the donor compound has a total carbon number of 3to 16, preferably of 4 to 16, especially of 4 to 12, in particular of 4to 8. In the specific case of the dihydrocarbyl ethers, preference isgiven in particular to those having a total of 6 to 14 and especially 8to 12 carbon atoms. In the specific case of the hydrocarbylcarboxylates, preference is given in particular to those having a totalof 3 to 10 and especially 4 to 6 carbon atoms.

The molar ratio of the donor compounds mentioned to the Lewis acids,i.e. specifically to the element halides and element alkyl halidesmentioned, especially to the Lewis acids BCl₃, AlCl₃, TiCl₄, FeCl₂,FeCl₃ and ZnCl₂, in the complex effective as a polymerization catalystgenerally varies within the range from 0.3:1 to 1.5:1, especially from0.5:1 to 1.2:1, in particular 0.7:1 to 1.1:1; in most cases it is 1:1.However, it is also possible to work with a greater excess of the donorcompounds, often up to a 10-fold and especially 3-fold molar excess; theexcess amount of donor compounds then acts additionally as a solvent ordiluent.

Typically, the complex effective as a polymerization catalyst isprepared separately prior to the polymerization from the Lewis acid(s)mentioned, which is/are generally used in anhydrous form, and the donorcompound(s), and is then—usually dissolved in an inert solvent such as ahalogenated hydrocarbon, for example dichloromethane—added to thepolymerization medium. However, the complex can also be prepared in situprior to the polymerization.

In a preferred embodiment of the present invention, the polymerizationis performed with additional use of at least one further initiator whichis mono- or polyfunctional, especially mono-, di- or trifunctional, andis selected from organic hydroxyl compounds, organic halogen compounds,protic acids and water. It is also possible to use mixtures of suchfurther initiators, for example mixtures of two or more organic hydroxylcompounds, mixtures of two or more organic halogen compounds, mixturesof one or more organic hydroxyl compounds and one or more organichalogen compounds, mixtures of one or more organic hydroxyl compoundsand water, mixtures of one or more organic halogen compounds and wateror mixtures of one or more protic acids and water. The initiator may bemono-, di- or polyfunctional, i.e. one, two or more hydroxyl groups orhalogen atoms, which start the polymerization reaction, may be presentin the initiator molecule. In the case of di- or polyfunctionalinitiators, telechelic isobutene polymers with two or more, especiallytwo or three, polyisobutene chain ends are typically obtained.

Organic hydroxyl compounds which have only one hydroxyl group in themolecule and are suitable as monofunctional initiators includeespecially alcohols and phenols, in particular those of the generalformula R⁵—OH, in which R⁵ denotes C₁- to C₂₀-alkyl radicals, especiallyC₁- to C₈-alkyl radicals, C₅- to C₈-cycloalkyl radicals, C₆- to C₂₀-arylradicals, especially C₆- to C₁₂-aryl radicals, or C₇- to C₂₀-arylalkylradicals, especially C₇- to C₁₂-arylalkyl radicals. In addition, the R⁵radicals may also comprise mixtures of the abovementioned structuresand/or have other functional groups than those already mentioned, forexample a keto function, a nitroxide or a carboxyl group, and/orheterocyclic structural elements.

Typical examples of such organic monohydroxyl compounds are methanol,ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol,tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol,2-ethylhexanol, cyclohexanol, phenol, p-methoxyphenol, o-, m- andp-cresol, benzyl alcohol, p-methoxybenzyl alcohol, 1- and2-phenylethanol, 1- and 2-(p-methoxyphenyl)ethanol, 1-, 2- and3-phenyl-1-propanol, 1-, 2- and 3-(p-methoxyphenyl)-1-propanol, 1- and2-phenyl-2-propanol, 1- and 2-(p-methoxyphenyl)-2-propanol, 1-, 2-, 3-and 4-phenyl-1-butanol, 1-, 2-, 3- and 4-(p-methoxyphenyl)-1-butanol,1-, 2-, 3- and 4-phenyl-2-butanol, 1-, 2-, 3- and4-(p-methoxyphenyl)-2-butanol, 9-methyl-9H-fluoren-9-ol,1,1-diphenylethanol, 1,1-diphenyl-2-propyn-1-ol, 1,1-diphenylpropanol,4-(1-hydroxy-1-phenylethyl)benzonitrile, cyclopropyldiphenylmethanol,1-hydroxy-1,1-diphenylpropan-2-one, benzilic acid, 9-phenyl-9-fluorenol,triphenylmethanol, diphenyl(4-pyridinyl)methanol,alpha,alpha-diphenyl-2-pyridinemethanol, 4-methoxytrityl alcohol(especially polymer-bound as a solid phase),alpha-tert-butyl-4-chloro-4′-methylbenzhydrol,cyclohexyldiphenylmethanol, alpha-(p-tolyl)-benzhydrol,1,1,2-triphenylethanol, alpha,alpha-diphenyl-2-pyridineethanol,alpha,alpha-4-pyridylbenzhydrol N-oxide, 2-fluorotriphenylmethanol,triphenylpropargyl alcohol, 4-[(diphenyl)hydroxy-methyl]benzonitrile,1-(2,6-dimethoxyphenyl)-2-methyl-1-phenyl-1-propanol,1,1,2-triphenylpropan-1-ol and p-anisaldehyde carbinol.

Organic hydroxyl compounds which have two hydroxyl groups in themolecule and are suitable as bifunctional initiators are especiallydihydric alcohols or diols having a total carbon number of 2 to 30,especially of 3 to 24, in particular of 4 to 20, and bisphenols having atotal carbon number of 6 to 30, especially of 8 to 24, in particular of10 to 20, for example ethylene glycol, 1,2- and 1,3-propylene glycol,1,4-butylene glycol, 1,6-hexylene glycol, 1,2-, 1,3- or1,4-bis(1-hydroxy-1-methylethyl)benzene (o-, m- or p-dicumyl alcohol),bisphenol A, 9,10-di-hydro-9,10-dimethyl-9,10-anthracenediol,1,1-diphenylbutane-1,4-diol, 2-hydroxytriphenylcarbinol and9-[2-(hydroxymethyl)phenyl]-9-fluorenol.

Organic halogen compounds which have one halogen atom in the moleculeand are suitable as monofunctional initiators are in particularcompounds of the general formula R⁶-Hal in which Hal is a halogen atomselected from fluorine, iodine and especially chlorine and bromine, andR⁶ denotes C₁- to C₂₀-alkyl radicals, especially C₁- to C₈-alkylradicals, C₅- to C₈-cycloalkyl radicals or C₇- to C₂₀-arylalkylradicals, especially C₇- to C₁₂-arylalkyl radicals. In addition, the R⁶radicals may also comprise mixtures of the abovementioned structuresand/or have other functional groups than those already mentioned, forexample a keto function, a nitroxide or a carboxyl group, and/orheterocyclic structural elements.

Typical examples of such monohalogen compounds are methyl chloride,methyl bromide, ethyl chloride, ethyl bromide, 1-chloropropane,1-bromopropane, 2-chloropropane, 2-bromopropane, 1-chlorobutane,1-bromobutane, sec-butyl chloride, sec-butyl bromide, isobutyl chloride,isobutyl bromide, tert-butyl chloride, tert-butyl bromide,1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane,1-chloroheptane, 1-bromoheptane, 1-chlorooctane, 1-bromooctane,1-chloro-2-ethylhexane, 1-bromo-2-ethylhexane, cyclohexyl chloride,cyclohexyl bromide, benzyl chloride, benzyl bromide,1-phenyl-1-chloroethane, 1-phenyl-1-bromoethane,1-phenyl-2-chloroethane, 1-phenyl-2-bromoethane,1-phenyl-1-chloropropane, 1-phenyl-1-bromopropane,1-phenyl-2-chloropropane, 1-phenyl-2-bromopropane,2-phenyl-2-chloropropane, 2-phenyl-2-bromopropane,1-phenyl-3-chloropropane, 1-phenyl-3-bromopropane,1-phenyl-1-chlorobutane, 1-phenyl-1-bromobutane,1-phenyl-2-chlorobutane, 1-phenyl-2-bromobutane,1-phenyl-3-chlorobutane, 1-phenyl-3-bromobutane,1-phenyl-4-chlorobutane, 1-phenyl-4-bromobutane,2-phenyl-1-chlorobutane, 2-phenyl-1-bromobutane,2-phenyl-2-chlorobutane, 2-phenyl-2-bromobutane,2-phenyl-3-chlorobutane, 2-phenyl-3-bromobutane, 2-phenyl-4-chlorobutaneand 2-phenyl-4-bromobutane.

Organic halogen compounds which have two halogen atoms in the moleculeand are suitable as difunctional initiators are, for example,1,3-bis(1-bromo-1-methylethyl)benzene, 1,3-bis(2-chloro-2-propyl)benzene(1,3-dicumyl chloride) and 1,4-bis(2-chloro-2-propyl)benzene(1,4-dicumyl chloride).

The further initiator is more preferably selected from organic hydroxylcompounds in which one or more hydroxyl groups are each bonded to ansp³-hybridized carbon atom, organic halogen compounds, in which one ormore halogen atoms are each bonded to an sp³-hybridized carbon atom,protic acids and water. Among these, preference is given in particularto an initiator selected from organic hydroxyl compounds in which one ormore hydroxyl groups are each bonded to an sp³-hybridized carbon atom.

In the case of the organic halogen compounds as further initiators,particular preference is further given to those in which the one or morehalogen atoms are each bonded to a secondary or especially to a tertiaryspa-hybridized carbon atom.

Preference is given in particular to further initiators which bear, onsuch an sp³-hydridized carbon atom, in addition to the hydroxyl group,the R⁵, R⁶ and R⁷ radicals, which are each independently hydrogen, C₁-to C₂₀-alkyl, C₅- to C₈-cycloalkyl, C₆- to C₂₀-aryl, C₇- toC₂₀-alkylaryl or phenyl, where any aromatic ring may also bear one ormore, preferably one two, C₁- to C₄-alkyl, C₁- to C₄-alkoxy, C₁- toC₄-hydroxyalkyl or C₁- to C₄-haloalkyl radicals as substituents, wherenot more than one of the variables R⁵, R⁶ and R⁷ is hydrogen and atleast one of the variables R⁵, R⁶ and R⁷ is phenyl which may also bearone or more, preferably one or two, C₁- to C₄-alkyl, C₁- to C₄-alkoxy,C₁- to C₄-hydroxyalkyl or C₁- to C₄-haloalkyl radicals as substituents.

Examples of useful protic acids include hydrochloric acid, hydrobromicacid, hydrofluoric acid, sulfuric acid, hydrocyanic acid and mixturesthereof. However, the protic acids used may also be protonated ethers.

For the present invention, very particular preference is given tofurther initiators selected from water, one or more protic acids,methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl)ethanol,n-propanol, isopropanol, 2-phenyl-2-propanol(cumene), n-butanol,isobutanol, sec-butanol, tert-butanol, 1-phenyl-1-chloroethane,2-phenyl-2-chloropropane(cumyl chloride), tert-butyl chloride and 1,3-or 1,4-bis(1-hydroxy-1-methylethyl)benzene and mixtures thereof. Amongthese, preference is given in particular to further initiators selectedfrom water, one or more protic acids, methanol, ethanol,1-phenylethanol, 1-(p-methoxy-phenyl)ethanol, n-propanol, isopropanol,2-phenyl-2-propanol(cumene), n-butanol, isobutanol, sec-butanol,tert-butano1,1-phenyl-1-chloroethane and 1,3- or1,4-bis(1-hydroxy-1-methylethyl)benzene and mixtures thereof.

The molar ratio of the sum of the organic sulfonic acids of the generalformula Z—SO₃H used in accordance with the invention and of any furtherinitiators to be used among those mentioned to the isobutene monomerused in the case of homopolymerization of isobutene, or to the totalamount of the polymerizable monomers used in the case ofcopolymerization of isobutene, based on each individual functional siteof the initiator (where the organic sulfonic acids should be consideredas monofunctional), is generally 0.001:1 to 0.5:1, especially 0.01:1 to0.4:1, in particular 0.1:1 to 0.3:1. When water is used as the solefurther initiator or in combination with organic hydroxyl compoundsand/or organic halogen compounds as further initiators, the molar ratioof water alone to the isobutene monomer used in the case ofhomopolymerization of isobutene, or to the total amount of thepolymerizable monomers used in the case of copolymerization of isobuteneis especially 0.0001:1 to 0.1:1, in particular 0.0002:1 to 0.05:1.

A proportion of the initiator molecules added as organic sulfonic acidsand optionally as organic hydroxyl or halogen compounds may beincorporated into the polymer chains. The proportion (I_(eff)) ofpolymer chains which are started by such an incorporated organicinitiator molecule may be up to 100%, is generally 0 to 90% and may be 5to 90%. The remaining polymer chains arise either from water originatingfrom traces of moisture as an initiator molecule, or from chain transferreactions.

In a further preferred embodiment of the present invention, thepolymerization is performed in the presence of 0.01 to 10 mmol,especially of 0.05 to 5.0 mmol, in particular of 0.1 to 1.0 mmol, basedin each case on 1 mol of isobutene monomer used in the case ofhomopolymerization of isobutene, or on 1 mol of the total amount of thepolymerizable monomers used in the case of copolymerization ofisobutene, of a basic nitrogen compound.

Such a basic nitrogen compound used may be an aliphatic, cycloaliphaticor aromatic amine of the general formula R⁷—NR⁸R⁹, or else ammonia, inwhich the variables R⁷, R⁸ and R⁹ are each independently hydrogen, C₁-to C₂₀-alkyl radicals, especially C₁- to C₈-alkyl radicals, C₅- toC₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals, especially C₆- toC₁₂-aryl radicals, or C₇- to C₂₀-arylalkyl radicals, especially C₇- toC₁₂-arylalkyl radicals. When none of these variables is hydrogen, theamine is a tertiary amine. When one of these variables is hydrogen, theamine is a secondary amine. When two of these variables is hydrogen, theamine is a primary amine. When all these variables are hydrogen, theamine is ammonia.

Typical examples of such amines of the general formula R⁷—NR⁸R⁹ aremethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,tert-butylamine, sec-butylamine, isobutylamine, tert-amylamine,n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine,cyclopentylamine, cyclohexylamine, aniline, dimethylamine, diethylamine,di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine,di-sec-butylamine, diisobutylamine, di-tert-amylamine, di-n-hexylamine,di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine,dicyclopentylamine, dicyclohexylamine, diphenylamine, trimethylamine,triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine,tri-tert-butylamine, tri-sec-butylamine, tri-isobutylamine,tri-tert-amylamine, tri-n-hexylamine, tri-n-heptylamine,tri-n-octylamine, tri-(2-ethylhexyl)amine, tricyclopentylamine,tricyclohexylamine, triphenylamine, dimethylethylamine,methyl-n-butylamine, N-methyl-N-phenylamine, N,N-dimethyl-N-phenylamine,N-methyl-N,N-diphenylamine or N-methyl-N-ethyl-N-n-butylamine.

In addition, such a basic nitrogen compound used may also be a compoundhaving a plurality of, especially having two or three, nitrogen atomsand having 2 to 20 carbon atoms, where these nitrogens may eachindependently bear hydrogen atoms or aliphatic, cycloaliphatic oraromatic substituents. Examples of such polyamines are1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine,diethylenetriamine, N-methyl-1,2-ethylenediamine,N,N-dimethyl-1,2-ethylenediamine, N,N′-dimethyl-1,2-ethylenediamine orN,N-dimethyl-1,3-propylenediamine.

However, a suitable basic nitrogen compound of this kind is especially asaturated, partly unsaturated or unsaturated nitrogen-containingfive-membered or six-membered heterocyclic ring which comprises one, twoor three ring nitrogen atoms and may have one or two further ringheteroatoms from the group of oxygen and sulfur and/or hydrocarbylradicals, especially C₁- to C₄-alkyl radicals and/or phenyl, and/orfunctional groups or heteroatoms as substituents, especially fluorine,chlorine, bromine, nitro and/or cyano, for example pyrrolidine, pyrrole,imidazole, 1,2,3- or 1,2,4-triazole, oxazole, thiazole, piperidine,pyrazane, pyrazole, pyridazine, pyrimidine, pyrazine, 1,2,3-, 1,2,4- or1,2,5-triazine, 1,2,5-oxathiazine, 2H-1,3,5-thiadiazine or morpholine.

However, a very particularly suitable basic nitrogen compound of thiskind is pyridine or a derivative of pyridine (especially a mono-, di- ortri-C₁- to C₄-alkyl-substituted pyridine) such as 2-, 3-, or4-methylpyridine (picolines), 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5- or3,6-dimethylpyridine (lutidines), 2,4,6-trimethylpyridine (collidine),2-, 3,- or 4-tert-butylpyridine, 2-tert-butyl-6-methylpyridine, 2,4-,2,5-, 2,6- or 3,5-di-tert-butylpyridine or else 2-, 3,- or4-phenylpyridine.

It is possible to use a single basic nitrogen compound or mixtures ofsuch basic nitrogen compounds.

For the use of isobutene or of an isobutene-comprising monomer mixtureas the monomer to be polymerized, suitable isobutene sources inembodiment (A) and (B) are both pure isobutene and isobutenic C₄hydrocarbon streams, for example C₄ raffinates, especially “raffinate1”, C₄ cuts from isobutane dehydrogenation, C₄ cuts from steam crackersand from FCC crackers (fluid catalyzed cracking), provided that theyhave been substantially freed of 1,3-butadiene present therein. A C₄hydrocarbon stream from an FCC refinery unit is also known as a “b/b”stream. Further suitable isobutenic C₄ hydrocarbon streams are, forexample, the product stream of a propylene-isobutane cooxidation or theproduct stream from a metathesis unit, which are generally used aftercustomary purification and/or concentration. Suitable C₄ hydrocarbonstreams generally comprise less than 500 ppm, preferably less than 200ppm, of butadiene. The presence of 1-butene and of cis- andtrans-2-butene is substantially uncritical. Typically, the isobuteneconcentration in the C₄ hydrocarbon streams mentioned is in the rangefrom 30 to 60% by weight. For instance, raffinate 1 generally consistsessentially of 30 to 50% by weight of isobutene, 10 to 50% by weight of1-butene, 10 to 40% by weight of cis- and trans-2-butene, and 2 to 35%by weight of butanes; in the polymerization process according to theinvention, the unbranched butenes in the raffinate 1 generally behavevirtually inertly, and only the isobutene is polymerized.

In a preferred embodiment, the monomer source used for thepolymerization is a technical C₄ hydrocarbon stream with an isobutenecontent of 1 to 100% by weight, especially of 1 to 99% by weight, inparticular of 1 to 90% by weight, more preferably of 30 to 60% byweight, especially a raffinate 1 stream, a b/b stream from an FCCrefinery unit, a product stream of a propylene-isobutane cooxidation ora product stream from a metathesis unit.

The isobutenic monomer mixture mentioned may comprise small amounts ofcontaminants such as water, carboxylic acids or mineral acids, withoutthere being any critical yield or selectivity losses. It is appropriateto prevent enrichment of these impurities by removing such harmfulsubstances from the isobutenic monomer mixture, for example byadsorption on solid adsorbents such as activated carbon, molecularsieves or ion exchangers.

It is also possible to convert monomer mixtures of isobutene or of theisobutenic hydrocarbon mixture with olefinically unsaturated monomerscopolymerizable with isobutene. When monomer mixtures of isobutene areto be copolymerized with suitable comonomers, the monomer mixturepreferably comprises at least 5% by weight, more preferably at least 10%by weight and especially at least 20% by weight of isobutene, andpreferably at most 95% by weight, more preferably at most 90% by weightand especially at most 80% by weight of comonomers.

Useful copolymerizable monomers include: vinylaromatics such as styreneand α-methylstyrene, C₁- to C₄-alkylstyrenes such as 2-, 3- and4-methylstyrene, and 4-tert-butylstyrene, halostyrenes such as 2-, 3- or4-chlorostyrene, and isoolefins having 5 to 10 carbon atoms, such as2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1,2-ethylhexene-1 and 2-propylheptene-1. Further useful comonomers includeolefins which have a silyl group, such as 1-trimethoxysilylethene,1-(trimethoxysilyl)propene,1-(trimethoxysilyl)-2-methylpropene-2,1-[tri(methoxyethoxy)silyl]ethene,1-[tri(methoxyethoxy)silyl]propene, and1-[tri(methoxyethoxy)silyl]-2-methylpropene-2. In addition—depending onthe polymerization conditions—useful comonomers also include isoprene,1-butene and cis- and trans-2-butene.

When the process according to the invention is to be used to preparecopolymers, the process can be configured so as to preferentially formrandom polymers or to preferentially form block copolymers. To prepareblock copolymers, for example, the different monomers can be suppliedsuccessively to the polymerization reaction, in which case the secondcomonomer is especially not added until the first comonomer is alreadyat least partly polymerized. In this manner, diblock, triblock andhigher block copolymers are obtainable, which, according to the sequenceof monomer addition, have a block of one or the other comonomer as aterminal block. In some cases, however, block copolymers also form whenall comonomers are supplied to the polymerization reactionsimultaneously, but one of them polymerizes significantly more rapidlythan the other(s). This is the case especially when isobutene and avinylaromatic compound, especially styrene, are copolymerized in theprocess according to the invention. This preferably forms blockcopolymers with a terminal polystyrene block. This is attributable tothe fact that the vinylaromatic compound, especially styrene,polymerizes significantly more slowly than isobutene.

The polymerization can be effected either continuously or batchwise.Continuous processes can be performed in analogy to known prior artprocesses for continuous polymerization of isobutene in the presence ofboron trifluoride-based catalysts in the liquid phase.

The process according to the invention is suitable either forperformance at low temperatures, e.g. at −90° C. to 0° C., or at highertemperatures, i.e. at at least 0° C., e.g. at 0° C. to +30° C. or at 0°C. to +50° C. The polymerization in the process according to theinvention is, however, preferably performed in embodiment (A) atrelatively low temperatures, generally at −70° C. to −10° C., especiallyat −60° C. to −15° C., and in embodiment (B) at slightly highertemperatures of −30° C. to +50° C., especially at 0° C. to +30° C., forexample at room temperature (+20 to +25° C.).

When the polymerization in the process according to the invention iseffected at or above the boiling temperature of the monomer or monomermixture to be polymerized, it is preferably performed in pressurevessels, for example in autoclaves or in pressure reactors.

The polymerization in the process according to the invention ispreferably performed in the presence of an inert diluent. The inertdiluent used should be suitable for reducing the increase in theviscosity of the reaction solution which generally occurs during thepolymerization reaction to such an extent that the removal of the heatof reaction which evolves can be ensured. Suitable diluents are thosesolvents or solvent mixtures which are inert toward the reagents used.Suitable diluents are, for example, aliphatic hydrocarbons such asn-butane, n-pentane, n-hexane, n-heptane, n-octane and isooctane,cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane,aromatic hydrocarbons such as benzene, toluene and the xylenes, andhalogenated hydrocarbons, especially halogenated aliphatic hydrocarbons,such as methyl chloride, dichloromethane and trichloromethane(chloroform), 1,1-dichloroethane, 1,2-dichloroethane, trichloroethaneand 1-chlorobutane and halogenated aromatic hydrocarbons andalkylaromatics halogenated in the alkyl side chains such aschlorobenzene, monofluoromethylbenzene, difluoromethylbenzene andtrifluoromethylbenzene, and mixtures of the aforementioned diluents.Preferred halogenated hydrocarbons for the inert diluents mentionedabove and below are chlorohydrocarbons, especially purechlorohydrocarbons. Fluorohydrocarbons are preferably excluded from theinert diluents usable here in order to very substantially rule outresidual contents of fluorine in the polymer. The diluents used, or theconstituents used in the solvent mixtures mentioned, are also the inertcomponents of isobutenic C₄ hydrocarbon streams.

According to embodiment (A), the inventive polymerization is preferablyperformed in a halogenated hydrocarbon, especially in a halogenatedaliphatic hydrocarbon, or in a mixture of halogenated hydrocarbons,especially of halogenated aliphatic hydrocarbons, or in a mixture of atleast one halogenated hydrocarbon, especially a halogenated aliphatichydrocarbon, and at least one aliphatic, cycloaliphatic or aromatichydrocarbon as an inert diluent, for example a mixture ofdichloromethane and n-hexane, typically in a volume ratio of 10:90 to90:10, especially of 50:50 to 85:15. Prior to use, the diluents arepreferably freed of impurities such as water, carboxylic acids ormineral acids, for example by adsorption on solid adsorbents such asactivated carbon, molecular sieves or ion exchangers.

In a further preferred variant of embodiment (A), the inventivepolymerization is performed in halogen-free aliphatic or especiallyhalogen-free aromatic hydrocarbons, especially toluene. For thisembodiment, water in combination with the organic hydroxyl compoundsmentioned and/or the organic halogen compounds mentioned, or especiallyas the sole initiator, have been found to be particularly advantageous.

According to embodiment (B), the inventive polymerization is preferablyperformed in an aliphatic, cycloaliphatic or aromatic hydrocarbon, in ahalogenated aliphatic hydrocarbon, or in a mixture of aliphatic,cycloaliphatic and/or aromatic hydrocarbons or of halogenated aliphatichydrocarbons, or in a mixture of at least one halogenated aliphatichydrocarbon and at least one aliphatic, cycloaliphatic or aromatichydrocarbon as an inert diluent.

The polymerization in the process according to the invention ispreferably performed under substantially aprotic and especially undersubstantially anhydrous reaction conditions. Substantially aprotic andsubstantially anhydrous reaction conditions are understood to mean that,respectively, the content of protic impurities and the water content inthe reaction mixture are less than 50 ppm and especially less than 5ppm. In general, the feedstocks will therefore be dried before use byphysical and/or chemical measures. More particularly, it has been foundto be useful to admix the aliphatic or cycloaliphatic hydrocarbons usedas solvents, after customary prepurification and predrying with anorganometallic compound, for example an organolithium, organomagnesiumor organoaluminum compound, in an amount which is sufficient tosubstantially remove the water traces from the solvent. The solvent thustreated is then preferably condensed directly into the reaction vessel.It is also possible to proceed in a similar manner with the monomers tobe polymerized, especially with isobutene or with the isobutenicmixtures. Drying with other customary desiccants such as molecularsieves or predried oxides such as aluminum oxide, silicon dioxide,calcium oxide or barium oxide is also suitable. The halogenated solventsfor which drying with metals such as sodium or potassium or with metalalkyls is not an option are freed of water or water traces withdesiccants suitable for that purpose, for example with calcium chloride,phosphorus pentoxide or molecular sieves. It is also possible in ananalogous manner to dry those feedstocks for which treatment with metalalkyls is likewise not an option, for example vinylaromatic compounds.Even if some or all of the initiator used is water, residual moistureshould preferably be very substantially or completely removed fromsolvents and monomers by drying prior to reaction, in order to be ableto use the water initiator in a controlled, specified amount, as aresult of which greater process control and reproducibility of theresults are obtained.

The polymerization of the isobutene or of the isobutenic startingmaterial generally proceeds spontaneously when the polymerizationcatalyst, i.e. the iron halide-donor complex, the aluminumtrihalide-donor complex or the alkylaluminum halide-donor complex,especially the iron chloride-donor complex or the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, is contactedwith the isobutene or the isobutenic monomer mixture at the desiredreaction temperature. The procedure here may be to initially charge themonomers, optionally in the diluent, to bring it to reaction temperatureand then to add the polymerization catalyst, i.e. the iron halide-donorcomplex, the aluminum trihalide-donor complex or the alkylaluminumhalide-donor complex, especially the iron chloride-donor complex or thealuminum trichloride-donor complex, or the at least one Lewis acidcomplex comprising organic sulfonic acids with or without donors. Theprocedure may also be to initially charge the polymerization catalyst,i.e. the iron halide-donor complex, the aluminum trihalide-donor complexor the alkylaluminum halide-donor complex, especially the ironchloride-donor complex or the aluminum trichloride-donor complex, or theat least one Lewis acid complex comprising organic sulfonic acids withor without donors, optionally in the diluent, and then to add themonomers. In that case, the start of polymerization is considered to bethat time at which all reactants are present in the reaction vessel.

To prepare isobutene copolymers, the procedure may be to initiallycharge the monomers, optionally in the diluent, and then to add thepolymerization catalyst, i.e. the iron halide-donor complex, thealuminum trihalide-donor complex or the alkylaluminum halide-donorcomplex, especially the iron chloride-donor complex or the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors. The reactiontemperature can be established before or after the addition of thepolymerization catalyst, i.e. the iron halide-donor complex, thealuminum trihalide-donor complex or the alkylaluminum halide-donorcomplex, especially of the iron chloride-donor complex or the aluminumtrichloride-donor complex, or of the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors. The proceduremay also be first to initially charge only one of the monomers,optionally in the diluent, then to add the polymerization catalyst, i.e.the iron halide-donor complex, the aluminum trihalide-donor complex orthe alkylaluminum halide-donor complex, especially the ironchloride-donor complex or the aluminum trichloride-donor complex, or theat least one Lewis acid complex comprising organic sulfonic acids withor without donors, and to add the further monomer(s) only after acertain time, for example when at least 60%, at least 80% or at least90% of the monomer has been converted. Alternatively, the polymerizationcatalyst, i.e. the iron halide-donor complex, the aluminumtrihalide-donor complex or the alkylaluminum halide-donor complex,especially the iron chloride-donor complex or the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, can beinitially charged, optionally in the diluent, then the monomers can beadded simultaneously or successively, and then the desired reactiontemperature can be established. In that case, the start ofpolymerization isconsidered to be that time at which the polymerizationcatalyst, i.e. the iron halide-donor complex, the aluminumtrihalide-donor complex or the alkylaluminum halide-donor complex,especially the iron chloride-donor complex, the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, and at leastone of the monomers are present in the reaction vessel.

In addition to the batchwise procedure described here, thepolymerization in the process according to the invention can also beconfigured as a continuous process. In this case, the feedstocks, i.e.the monomer(s) to be polymerized, optionally the diluent and optionallythe polymerization catalyst, i.e. the iron halide-donor complex, thealuminum trihalide-donor complex or the alkylaluminum halide-donorcomplex, especially the iron chloride-donor complex or the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, are suppliedcontinuously to the polymerization reaction, and reaction product iswithdrawn continuously, such that more or less steady-statepolymerization conditions are established in the reactor. The monomer(s)to be polymerized can be supplied as such, diluted with a diluent orsolvent, or as a monomer-containing hydrocarbon stream.

The iron halide-donor complex effective as a polymerization catalyst,the aluminum trihalide-donor complex or the alkylaluminum halide-donorcomplex, especially the iron chloride-donor complex or the aluminumtrichloride-donor complex, or the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, is generallypresent in dissolved, dispersed or suspended form in the polymerizationmedium. Supporting of the iron halide-donor complex, of the aluminumtrihalide-donor complex or of the alkylaluminum halide-donor complex,especially of the iron chloride-donor complex or of the aluminumtrichloride-donor complex, or of the at least one Lewis acid complexcomprising organic sulfonic acids with or without donors, on customarysupport materials is also possible. Suitable reactor types for thepolymerization process of the present invention are typically stirredtank reactors, loop reactors and tubular reactors, but also fluidizedbed reactors, stirred tank reactors with or without solvent, fluid bedreactors, continuous fixed bed reactors and batchwise fixed bed reactors(batchwise mode).

In the process according to the invention, the iron halide-donor complexeffective as a polymerization catalyst, the aluminum trihalide-donorcomplex or the alkylaluminum halide-donor complex, especially the ironchloride-donor complex or the aluminum trichloride-donor complex, or theat least one Lewis acid complex comprising organic sulfonic acids withor without donors, is generally used in such an amount that the molarratio of element of transition groups 1 to 8 or of main groups 3 to 5 ofthe Periodic Table of the Elements, especially of iron and aluminum inthe iron halide-donor complex, aluminum trihalide-donor complex oralkylaluminum halide-donor complex, especially in the iron halide-donorcomplex or aluminum trichloride-donor complex, or in the correspondingat least one organic sulfonic acid-comprising Lewis acid complex with orwithout donors, to isobutene in the case of homopolymerization ofisobutene, or to the total amount of the polymerizable monomers used inthe case of copolymerization of isobutene, is in the range from 1:10 to1:5000, especially 1:15 to 1:1000, in particular 1:20 to 1:250.

To stop the reaction, the reaction mixture is preferably deactivated,for example by adding a protic compound, especially by adding water,alcohols such as methanol, ethanol, n-propanol and isopropanol ormixtures thereof with water, or by adding an aqueous base, for examplean aqueous solution of an alkali metal or alkaline earth metal hydroxidesuch as sodium hydroxide, potassium hydroxide, magnesium hydroxide orcalcium hydroxide, an alkali metal or alkaline earth metal carbonatesuch as sodium, potassium, magnesium or calcium carbonate, or an alkalimetal or alkaline earth metal hydrogencarbonate such as sodium,potassium, magnesium or calcium hydrogencarbonate.

In the process according to the invention, for the derivatization byintroduction of the low molecular weight polar groups A, the describedhigh-reactivity isobutene homo- or copolymers with a content of terminalvinylidene double bonds (α-double bonds) per polyisobutene chain end ofat least 50 mol %, preferably of at least 60 mol %, preferably of atleast 70 mol %, preferably of at least 80 mol %, preferably of at least85 mol %, more preferably of at least 90 mol %, even more preferably ofmore than 91 mol % and especially of at least 95 mol %, for example ofvirtually 100 mol %, are used. More particularly, high-reactivityisobutene copolymers which are formed from isobutene and at least onevinylaromatic monomer, especially styrene, and have a content ofterminal vinylidene double bonds (α-double bonds) per polyisobutenechain end of at least 50 mol %, preferably of at least 60 mol %,preferably of at least 70 mol %, preferably of at least 80 mol %,preferably of at least 85 mol %, more preferably of at least 90 mol %,even more preferably of more than 91 mol % and especially of at least 95mol %, for example of virtually 100 mol %. To prepare such copolymers ofisobutene and at least one vinylaromatic monomer, especially styrene,isobutene or an isobutenic hydrocarbon cut is copolymerized with the atleast one vinylaromatic monomer in a weight ratio of isobutene tovinylaromatic of 5:95 to 95:5, especially of 30:70 to 70:30.

The high-reactivity isobutene homo- or copolymers used according to theinvention and specifically the isobutene homopolymers preferably have apolydispersity (PDI=M_(w)/M_(n)) of 1.05 to less than 3.5, preferably of1.05 to less than 3.0, preferably of 1.05 to less than 2.5, preferablyof 1.05 to 2.3, more preferably of 1.05 to 2.0 and especially of 1.1 to1.85. Typical PDI values in the case of an optimal process regime are1.2 to 1.7.

The high-reactivity isobutene homo- or copolymers used according to theinvention preferably possess a number-average molecular weight M_(n)(determined by gel permeation chromatography) of preferably 500 to 250000, more preferably of 500 to 100 000, even more preferably of 500 to25 000 and especially of 500 to 5000. Isobutene homopolymers even morepreferably possess a number-average molecular weight M_(n) of 500 to 10000 and especially of 500 to 5000, for example of about 1000 or of about2300.

More particularly, the process according to the invention is suitablefor preparing isobutene homo- or copolymer derivatives of the generalformula I, in which the parent hydrophobic n-functional radical of thePOL has been formed by homopolymerizing isobutene or copolymerizingisobutene with up to 20% by weight of n-butene, is monofunctional andhas a number-average molecular weight (M_(n)) of 500 to 5000, inparticular 650 to 2500.

More particularly, the process according to the invention isadditionally also suitable for preparing isobutene homo- or copolymerderivatives of the general formula I, in which the parent hydrophobicn-functional radical of the POL has been formed by homopolymerizingisobutene or copolymerizing isobutene with up to 20% by weight ofn-butene, in each case with additional use of a di- or trifunctionalinitiator (Inifer), is di- or trifunctional and has a number-averagemolecular weight (M_(n)) of 500 to 10 000, in particular 1000 to 5000.

More particularly, the process according to the invention isadditionally also suitable for preparing isobutene copolymer derivativesof the general formula I, in which the parent hydrophobic n-functionalradical of the POL has been formed by copolymerizing isobutene with atleast one vinylaromatic comonomer, optionally with additional use of adi- or trifunctional initiator (Inifer), is mono-, di- or trifunctionaland has a number-average molecular weight (M_(n)) of 500 to 15 000, inparticular 1000 to 10 000.

In a preferred embodiment of the process according to the invention forpreparing isobutene homo- or copolymer derivatives of the generalformula I, the low molecular weight polar A group is one selected from

-   -   (a) mono- or polyamino groups having up to 6 nitrogen atoms,        where at least one nitrogen atom has basic properties;    -   (b) nitro groups, optionally in combination with hydroxyl        groups;    -   (c) hydroxyl groups, optionally in combination with mono- or        polyamino groups, where at least one nitrogen atom has basic        properties;    -   (d) carboxyl groups or the alkali metal or alkaline earth metal        salts thereof;    -   (e) sulfo groups or the alkali metal or alkaline earth metal        salts thereof;    -   (f) polyoxy-C₂-C₄-alkylene moieties terminated by hydroxyl        groups, mono- or polyamino groups, where at least one nitrogen        atom has basic properties, or by carbamate groups;    -   (g) carboxylic ester groups;    -   (h) succinic anhydride or moieties which are derived from        succinic anhydride and have hydroxyl and/or amino and/or        quaternized amino and/or amido and/or imido groups, which have        been prepared by thermal or halogen-catalyzed maleation of the        internal double bond(s) and of the terminal vinylidene double        bond(s) of the parent polyisobutene homo- or copolymers of the        POL with maleic anhydride and, in the case of moieties which are        derived from succinic anhydride and have hydroxyl and/or amino        and/or quaternized amino and/or amido and/or imido groups, by        appropriate further reactions, and any resulting carboxamide or        carboximide derivative can be modified by further reaction with        at least one C₂- to C₁₂-dicarboxylic anhydride, with at least        one C₂- to C₄-alkylene carbonate and/or with boric acid;    -   (j) moieties obtained by Mannich reaction of POL-substituted        phenols with aldehydes and mono- or polyamines;    -   (k) phenol, alkylphenol or (hydroxyalkyl) phenol moieties;    -   (l) hydroxymethyl groups;    -   (m) moieties which have been obtained by epoxidation of the        terminal vinylidene double bond(s) of the parent polyisobutene        homo- or copolymers of the POL and subsequent        -   (i) hydrolysis to the 1,2-diol,        -   (ii) reaction with a thiol or a polythiol,        -   (iii) reaction with ammonia, a monoamine or a polyamine,        -   (iv) reaction with a borane to give a borate ester and            oxidative cleavage of the borate ester to the 1,3-diol,        -   (v) conversion to an aldehyde,        -   (vi) conversion to an aldehyde and conversion of the            aldehyde to an oxime and reduction of the oxime to the            amine,        -   (vii) conversion to an aldehyde and conversion of the            aldehyde to an azomethine cation and hydrolysis to the            amine,        -   (viii) conversion to an aldehyde and conversion of the            aldehyde to an alcohol or        -   (ix) conversion to an aldehyde and conversion of the            aldehyde to a Schiff base or an enamine, and reduction of            the Schiff base or of the enamine to the amine;    -   (n) moieties which have been obtained by hydroboration of the        terminal vinylidene double bond(s) of the parent polyisobutene        homo- or copolymers of the POL and subsequent oxidation of the        primary hydroboration product; and    -   (o) moieties which have been obtained by hydrosilylation of the        terminal vinylidene double bond(s) of the parent polyisobutene        homo- or copolymers of the POL.

Examples of the above low molecular weight polar A groups include thefollowing:

Isobutene homo- or copolymer derivatives which comprise mono- orpolyamino groups (a) and are of the general formula I are basedgenerally on high-reactivity poly-isobutene having predominantlyterminal vinylidene double bonds, especially on those having anumber-average molecular weight M_(n) of 300 to 5000. They may alsocomprise proportions of internal double bonds. Polyisobuteneamines basedon high-reactivity polyisobutene which may comprise up to 20% by weightof n-butene units are obtainable, for example, according to EP-A 244 616by hydroformylation and reductive amination with ammonia, monoamines orpolyamines such as dimethylaminopropyl-amine, ethylenediamine,diethylenetriamine, triethylenetetramine or tetraethylene-pentamine.When the preparation of the isobutene homo- or copolymer derivatives Iproceeds from polyisobutene having a proportion of internal double bonds(usually in the β- and γ position), another option is the preparationroute by chlorination and subsequent amination or by oxidation of thedouble bond with air or ozone to give the carbonyl or carboxyl compound,and subsequent amination under reductive (hydrogenating) conditions. Forthe amination, it is possible here to use amines, for example ammonia,monoamines or polyamines, such as dimethylaminopropylamine,ethylenediamine, diethylenetriamine, triethylenetetramine ortetraethylenepentamine.

Further preferred isobutene homo- or copolymer derivatives I comprisingmonoamino groups (a) are the hydrogenation products of the reactionproducts formed from polyisobutenes having a mean degree ofpolymerization P=5 to 100 with nitrogen oxides or mixtures of nitrogenoxides and oxygen, as described especially in WO-A-97/03946.

Further preferred isobutene homo- or copolymer derivatives I comprisingmonoamino groups (a) are the compounds obtainable from polyisobuteneepoxides by reaction with amines and subsequent dehydration andreduction of the amino alcohols, as described especially in DE-A-196 20262.

Further preferred isobutene homo- or copolymer derivatives I comprisingmonoamino groups (a) are the compounds obtainable from the reaction ofhigh-reactivity polyisobutene with one or more aromatic orheteroaromatic amines. The high-reactivity polyisobutene can beconverted for this purpose with aniline, N-methylaniline,N,N-dimethylaniline, o-, m- or p-toluidine or o-, m- or p-aminopyridineto the corresponding compound polyisobutyl-substituted on the aromaticor heteroaromatic ring, for example. The aromatic amines used may alsobe polysubstituted, especially disubstituted, on the ring, especially byalkyl groups, for example C₁- to C₄-alkyl groups; typical substitutionpatterns for such substituents on the aromatic ring are the 2,3, 2,4,2,5, 2,6, 3,4 or 3,5 arrangements. Examples of typical compounds formedhere are 4-polyisobutylaniline, 4-polyisobutyl-N-methylaniline,4-polyisobutyl-N,N-dimethylaniline, 4-polyisobutyl-3-methylaniline or5-polyisobutyl-2-aminopyridine. Such compounds polyisobutyl-substitutedon the aromatic or heteroaromatic ring are generally synthesized by thecustomary methods of electrophilic aromatic substitution (Friedel-Craftsalkylation) on the aromatic or heteroaromatic ring, for example usingLewis acids such as AlCl₃, ZnCl₂ or BF₃ as catalysts, and at elevatedtemperatures, especially 25 to 80° C., if required in an inert solvent.

Isobutene homo- or copolymer derivatives I comprising nitro groups (b),optionally in combination with hydroxyl groups, are preferably reactionproducts formed from polyisobutenes of mean degree of polymerization P=5to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxidesand oxygen, as described especially in WO-A-96/03367 and WO-A-96/03479.These reaction products are generally mixtures of purenitropolyisobutenes (e.g. α,β-dinitropolyisobutene) and mixedhydroxynitropoly-isobutenes (e.g. α-nitro-β-hydroxypolyisobutene).

Isobutene homo- or copolymer derivatives I comprising hydroxyl groups incombination with mono- or polyamino groups (c) are especially reactionproducts of polyisobutene epoxides, obtainable from polyisobutene whichpreferably has predominantly terminal double bonds and has M_(n)=300 to5000, with ammonia, mono- or polyamines, as described especially inEP-A-476 485. Isobutene homo- or copolymer derivatives I which comprisehydroxyl groups (c) and do not have any mono- or polyamino groups are,for example, reaction products of polyisobutene epoxides, obtainablefrom polyisobutene which preferably has predominantly terminal doublebonds and has M_(n)=300 to 5000, with water (hydrolysis) or withalcohols such as methanol or ethanol, or the products of a reduction ofthe epoxy function, for example by means of lithium-aluminum hydride.

Isobutene homo- or copolymer derivatives I comprising carboxyl groups orthe alkali metal or alkaline earth metal salts thereof (d) are generallypolyisobutenes into which one or more carboxyl groups have beenintroduced, for example by reaction with maleic anhydride, and all orsome of the carboxyl groups have then been converted to the alkali oralkaline earth metal salts and any remainder of the carboxyl groups hasbeen reacted with alcohols or amines.

Isobutene homo- or copolymer derivatives I comprising sulfo groups orthe alkali metal or alkaline earth metal salts thereof (e) are generallypolyisobutenes into which one or more sulfo groups have been introduced,and all or some of the sulfo groups have then been converted to thealkali metal or alkaline earth metal salts and any remainder of thecarboxyl groups has been reacted with alcohols or amines. Analogousalkali metal or alkaline earth metal salts of alkyl sulfosuccinates aredescribed in EP-A-639 632. Such compounds serve principally to preventvalve seat wear and can be used advantageously in combination withcustomary fuel detergents such as poly(iso)buteneamines or polyetheramines.

Isobutene homo- or copolymer derivatives I comprisingpolyoxy-C₂-C₄-alkylene moieties (f) are preferably polyethers orpolyether amines, which are obtainable by reacting hydroxyl- oramino-containing polyisobutenes with 1 to 30 mol of ethylene oxideand/or propylene oxide and/or butylene oxide per hydroxyl group or aminogroup and—in the case of polyetheramines—by subsequent reductiveamination with ammonia, monoamines or polyamines. Analogous reactionproducts of C₂-C₆₀-alkanols, C₆-C₃₀-alkanediols, mono- ordi-C₂-C₃₀-alkylamines, C₁-C₃₀-alkylcyclohexanols or C₁-C₃₀-alkylphenolswith 1 to 30 mol of ethyleneoxide and/or propyleneoxid and/orbutyleneoxide per hydroxyl group or amino group are described inEP-A-310 875, EP-A-356 725, EP-A-700 985 and U.S. Pat. No. 4,877,416.

Isobutene homo- or copolymer derivatives I comprising carboxylic estergroups (g) are preferably esters of mono-, di- or tricarboxylic acidswith hydroxyl-containing polyisobutenes. Analogous reaction products oflong-chain alkanols or polyols with mono-, di- or tricarboxylic acidsare described in DE-A-38 38 918. The mono-, di- or tricarboxylic acidsused may be aliphatic or aromatic acids. Typical representatives of suchesters are corresponding adipates, phthalates, isophthalates,terephthalates and trimellitates.

Isobutene homo- or copolymer derivatives I comprising succinic anhydride(h) are especially polyisobutenylsuccinic anhydrides, which areobtainable by reaction of high-reactivity polyisobutene with M_(n)=500to 5000 with maleic anhydride by a thermal route or via the chlorinatedpolyisobutene. The polyisobutene used may be reacted with 1 equivalent(“monomaleation”), with two equivalents of maleic anhydride(“bismaleation”) or with 1<n<2 equivalents of maleic anhydride, forexample with 1.05 to 1.3 equivalents of maleic anhydride.

Isobutene homo- or copolymer derivatives I comprising moieties whichderive from succinic anhydride and have hydroxyl and/or amino and/orquaternized amino and/or imido groups (h) are preferably correspondingderivatives of polyisobutyl- or polyisobutenyl-substituted succinicanhydride and especially the corresponding derivatives ofpolyisobutenylsuccinic anhydride which are obtainable by reaction ofhigh-reactivity polyisobutene with M_(n)=300 bis 5000, which may stillcomprise proportions of internal double bonds, with maleic anhydride bya thermal route or via the chlorinated polyisobutene. Of particularinterest in this context are derivatives with alcohols such as methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol,tert-butanol or polyethers which have been prepared by alkoxylation ofthe low molecular weight alcohols mentioned with C₂- to C₄-alkyleneoxides. Isobutenic C₄ hydrocarbon streams and in particular aliphaticpolyamines such as ethylenediamine, diethylenetriamine,triethylenetetramine or tetraethylenepentamine. The moieties withhydroxyl, optionally quaternized amino, amido and/or imido groups are,for example, carboxylic acid groups, acid amides of monoamines, acidamides of di- or polyamines which, as well as the amide function, alsohave free amine groups, succinic acid derivatives with an acid and anamide function, carboximides with monoamines, carboxyimides with di- orpolyamines which, as well as the imide function, also have free aminegroups, or diimides which are formed by the reaction of di- orpolyamines with two succinic acid derivatives. Such compounds have beendescribed as fuel additives in U.S. Pat. No. 4,849,572.

Isobutene homo- or copolymer derivatives I comprising moieties whichderive from succinic anhydride and have quaternized amino groups areunderstood to mean especially quaternized nitrogen compounds which areobtainable by addition of a compound comprising at least one oxygen- ornitrogen-containing group reactive with anhydride and additionally atleast one quaternizable amino group onto polyisobutenylsuccinicanhydride, and subsequent quaternization, especially with an epoxide,especially in the absence of free acid, as described in EP patentapplication 10 168 622.8. Suitable compounds having at least one oxygen-or nitrogen-containing group reactive with an anhydride and additionallyat least one quaternizable amino group are especially polyamines havingat least one primary or secondary amino group and at least one tertiaryamino group. Such a quaternized nitrogen compound is, for example, thereaction product, obtained at 40° C., of polyisobutenylsuccinicanhydride in which the polyisobutenyl radical typically has an M_(n) of1000 with 3-(dimethylamino)-propylamine, which is apolyisobutenylsuccinic monoamide and which is subsequently quaternizedwith styrene oxide in the absence of free acid at 70° C.

The resulting carboxamide and carboximide derivatives in group (h) can,especially in the case of use in lubricant formulations, to improve theswelling behavior of elastomers which are incorporated, for example, inseals of engines, units or devices which come into contact with thederivatives mentioned or with lubricant formulations comprising them,also be modified with at least one C₂- to C₁₂-dicarboxylic anhydridesuch as maleic anhydride or phthalic anhydride, with at least one C₂- toC₄-alkylene carbonate such as ethylene carbonate or propylene carbonate,and/or with boric acid.

Isobutene homo- or copolymer derivatives I which comprise moieties (j)obtained by Mannich reaction of substituted phenols with aldehydes andmono- or polyamines are preferably reaction products ofpolyisobutyl-substituted phenols with aldehydes such as formaldehyde,which can also be used, for example, in oligomeric or polymeric form,for example as paraformaldehyde, and with monoamines, e.g.dimethylamine, diethylamine, propylamine, butylamine or morpholine, orwith polyamines, e.g. ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine ordimethylaminopropylamine. The polyisobutyl-substituted phenols may, inaddition to the terminal vinylidene double bonds, also compriseproportions of internal double bonds. Such “polyisobutene Mannich bases”based on high-reactivity polyisobutene with M_(n)=300 to 5000 aredescribed in EP-A-831 141.

Isobutene homo- or copolymer derivatives I comprising phenol,alkylphenol or (hydroxyalkyl)phenol moieties (k) are especially theprecursors to the polyisobutene Mannich bases in group (j), which areformed by reaction of high-reactivity polyisobutene with one or moreappropriate phenols, optionally with subsequent reaction with analdehyde. For this purpose, the high-reactivity polyisobutene can bereacted, for example, with unsubstituted phenol, o-, m- or p-cresol,xylenol, hydroquinone, catechol or resorcinol. Polyisobutyl-substitutedphenol thus formed can, for example, be converted further with analdehyde, such as formaldehyde or paraformaldehyde, to apolyisobutyl-substituted hydroxyalkylphenol, especially apolyisobutyl-substituted hydroxymethylphenol, for example to1-hydroxymethyl-4-polyisobutylphenol.

Isobutene homo- or copolymer derivatives I comprising hydroxymethylgroups (I) are especially the intermediates in the hydroformylation ofhigh-reactivity polyisobutene according to EP-A 244 616 in the presenceof carbon monoxide and hydrogen by means of a suitable hydroformylationcatalyst such as a rhodium or cobalt catalyst at temperatures of 80 to200° C. and CO/H₂ pressures of up to 600 bar. Ahydroxymethyl-polyisobutene thus obtained can be obtained as a productmixture together with a polyisobutene comprising an aldehyde group.

The moieties which are listed in group (m) under (i) to (ix) and may bepresent in the isobutene homo- or copolymer derivatives I, and theproduction thereof, are described in detail in the context of furtherreactions of isobutene polymer epoxides, for example in WO 2007/025700,and are reproduced below:

The epoxide can, for example, be hydrolyzed with water to give 1,2-diolsor reacted with thiols or primary or secondary amines to obtain, interalia, glycol thioethers and amines.

Reaction of an isobutene polymer which, on average, has at least 0.7,preferably at least 0.9, epoxy group per molecule with polyols orespecially polythiols, such as trimethylolpropanetris(3-mercaptopropionate) or pentaerythrityltetrakis(3-mercapto-propionate), or polyamines, such asdiethylenetriamine, affords networks which are advantageous owing totheir elastic and damping properties.

In a preferred further reaction, the epoxide is rearranged to thealdehyde, which can be done, for example, with catalysis by means ofaluminosilicates, for example, zeolites, acidic alumina, Lewis acidssuch as aluminum or zinc salts, e.g. zinc bromide, or protic acids suchas sulfuric acid. The aldehyde is in turn a versatile starting materialfor valuable products. The conversion of polyisobutenyl epoxides toaldehydes is described, for example, in WO 90/10022 and U.S. Pat. No.6,303,703, or Organikum, 20th ed. 1999, Wiley-VCH, p. 615.

The aldehyde can be converted to an imine with ammonia or a primaryamine, and the imine can be reduced, especially catalyticallyhydrogenated, to the amine. Suitable primary amines are, for example,diethylenetriamine, di(methylethylene)triamine, triethylenetetramine,tri(methylethylene)tetramine, tri(ethylethylene)tetramine,tetraethylenepentamine, pentaethylenehexamine, ethylenediamine,hexamethylenediamine, o-phenylenediamine, m-phenylenediamine,p-phenylenediamine, alkyl-substituted o-, m- and p-phenylenediamine,dimethylaminomethylamine, dimethylaminoethylamine,dimethylaminopropylamine, dimethylaminobutylamine,dimethylaminoheptylamine, diethylaminomethylamine,diethylaminopropylamine, diethylaminoamylamine,dipropylaminopropylamine, methylpropylaminoamylamine,propylbutylaminoethylamine, dimethylenetrianiline, methylenedianiline,polymethyleneaniline, and polyalkylmethyleneaniline. The reaction of thealdehyde with the primary amine and the hydrogenation of the resultingimine to a polyisobutenylamine is described in WO 90/10022.

The aldehyde can also be converted to an oxime, and the oxime reduced tothe amine. Appropriately, hydroxylamine, which is obtained byneutralizing a hydroxylammonium salt, is used. The hydroxylamine reactswith the aldehyde to give the oxime. The oxime is then reduced bycatalytic hydrogenation to the amine. The hydrogenation is effected atsuitable temperature and pressure in the presence of a hydrogenationcatalyst. Suitable catalysts are, for example Raney nickel, nickel onkieselguhr, copper chromite, platinum on carbon, palladium on carbon andthe like. The reaction is described, for example in U.S. Pat. No.6,303,703.

In a further preferred embodiment, the aldehyde is converted to anazomethine cation in a Leuckart reaction. To perform the Leuckartreaction, various reagents are suitable; ammonium formate is preferred.The azomethine cation can then be converted to an amine by hydrolysis.The hydrolysis can suitably be performed with dilute hydrochloric acidat moderately elevated temperature. Preference is given to using a phasetransfer catalyst such as tricaprylylmethylammonium nitrate. Thereaction is described, for example in U.S. Pat. No. 6,303,703.

The epoxide can additionally be converted to a 1,3-diol, for example to2-polyisobutenyl-1,3-propanediol, by reaction with a borane andsubsequent oxidative cleavage of the borate ester formed. Suitableboranes are, for example, diborane (B₂H₆) and alkyl- and arylboranes. Itis familiar to the person skilled in the art that such boranes can alsobe prepared in situ from a borohydride and an acid, usually BF₃etherate. The reaction with the borane is effected suitably in aborane-coordinating solvent. Examples thereof are open-chain ethers suchas dialkyl ethers, diaryl ethers or alkyl aryl ethers, and cyclicethers, such as tetrahydrofuran or 1,4-dioxane, but solvents such astoluene, cyclohexane, and methylene chloride are also suitable. Theoxidative cleavage to give the 1,3-diol can be effected, for example, bymeans of hydrogen peroxide in the presence of a base with heating to,for example, from 50 to 75° C. Suitable solvents for this purpose areethers or mixtures of ethers and hydrocarbons.

Moieties (n) which result from hydroboration reactions and may bepresent in the isobutene homo- or copolymer derivatives I, and theproduction thereof, are described in detail, for example, in WO2004/067583. General fundamentals of hydroboration are described in J.March, Advanced Organic Chemistry, 4th edition, Verlag J. Wiley & Sons,p. 783-789.

The suitable borane sources include in particular borane (BH₃) itself,which typically occurs in the form of the dimer thereof (B₂B₆).Appropriately, the borane is obtained in situ by reaction of suitableprecursors, especially of alkali metal or alkaline earth metal salts ofthe BH₄ anion with boron trihalides. Typically, sodium borohydride andboron trifluoride etherate are used here.

A preferred hydroboration agent for the terminal vinylidene double bondsof the polyisobutene is the reaction product of a borane source, forexample borane obtained in situ from alkali metal or alkaline earthmetal salts of the BH₄ anion with boron trihalides, with 0.5 to 1.8equivalents per mole of borane of an alkene of molecular weight lessthan 250, for example 2-methyl-2-butene or 1-methylcyclohexene.

The subsequent oxidation of the primary hydroboration product iseffected typically with alkaline hydrogen peroxide to obtain an alcohol,which preferably corresponds in formal terms to the anti-Markovnikovhydration product of the unsaturated isobutene polymer. Alternatively,the polyisobutylboranes obtained as the primary hydroboration productcan also be subjected to an oxidative reaction with bromine in thepresence of hydroxide ions to obtain the bromide.

Moieties (o) which result from hydrosilylation reactions and may bepresent in the isobutene homo- or copolymer derivatives I, and theproduction thereof, are described in detail, for example, in WO2003/074577. For this purpose, a high-reactivity polyisobutene can besubjected to a reaction with a silane in the presence of a silylationcatalyst to obtain a polyisobutene at least partly functionalized withsilyl groups. Silylated isobutene polymers are again valuable startingmaterials for further conversions to novel products, for example formoisture-curing sealing compounds and for formulations in which glassadhesion is important.

Suitable hydrosilylation catalysts are especially transition metalcatalysts where the transition metal is selected from Pt, Pd, Rh, Ru andIr, for example finely divided platinum, platinum chloride,hexachloroplatinic acid, tetramethyldivinyldisiloxane-platinumcomplexes, RhCl[P(C₆H₅)₃], RhCl₃, RuCl₃ or IrCl₃. Suitablehydrosilylation catalysts are additionally Lewis acids such as aluminumtrichloride or titanium tetrachloride, and peroxides.

Suitable silanes are, for example, halogenated silanes such astrichlorosilane, methyldichlorosilane, dimethylchlorosilane andtrimethylsiloxydichlorosilane, alkoxysilanes such as trimethoxysilane,triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane,1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane and acyloxysilanes.

The reaction temperature in the hydrosilylation is preferably in therange from 0 to 140° C., especially 40 to 120° C. The reaction istypically performed at standard pressure, but can also be effected atelevated pressures, for example at 1.5 to 20 bar, or reduced pressure,for example at 200 to 600 mbar. The reaction can be effected withoutsolvent or in the presence of a suitable inert solvent such as toluene,tetrahydrofuran or chloroform.

In a preferred embodiment, the process according to the invention forpreparing isobutene homo- or copolymer derivatives of the generalformula I in which A is a low molecular weight polar group whichcomprises an amino function is performed by polymerizing isobutene or anisobutene-comprising monomer mixture in the presence

-   -   (A) of an iron halide-donor complex effective as a        polymerization catalyst, of an aluminum trihalide-donor complex        or of an alkylaluminum halide-donor complex which comprises, as        the donor, an organic compound with at least one ether function        or a carboxylic ester function, in particular with additional        use of an initiator, or    -   (B) of at least one Lewis acid suitable as a polymerization        catalyst or of a complex which is effective as a polymerization        catalyst and is formed from at least one Lewis acid and at least        one donor, and in the presence of at least one initiator, using        as the at least one initiator an organic sulfonic acid of the        general formula Z—SO₃H in which the variable Z denotes a C₁- to        C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to        C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇- to        C₂₀-arylalkyl radical,

hydroformylating the resulting high-reactivity isobutene homo- orcopolymer with a suitable catalyst in the presence of carbon monoxideand hydrogen, and then reductively aminating in the presence of at leastn equivalents of ammonia or of a mono- or polyamine.

The hydroformylation and the reductive amination of high-reactivitypolyisobutenes are described, for example, in EP-A 244 616. In thiscase, the hydroformylation is performed in the presence of carbonmonoxide and hydrogen, typically by means of a suitable hydroformylationcatalyst such as a rhodium or cobalt catalyst, at temperatures of 80 to200° C. and CO/H₂ pressures of up to 600 bar. The subsequent reductiveamination of the oxo product obtained (hydroxymethylpolyisobutene orproduct mixture of hydroxymethylpolyisobutene and polyisobutenealdehydeof the same carbon number) is effected generally at temperatures of 80to 200° C. and hydrogen pressures of up to 600 bar, especially 80 to 300bar.

In a further preferred embodiment, the process according to theinvention for preparing isobutene homo- or copolymer derivatives of thegeneral formula I in which A is a low molecular weight polar group whichcomprises an amino function is performed by polymerizing isobutene or anisobutene-comprising monomer mixture in the presence

-   -   (A) of an iron halide-donor complex effective as a        polymerization catalyst, of an aluminum trihalide-donor complex        or of an alkylaluminum halide-donor complex which comprises, as        the donor, an organic compound with at least one ether function        or a carboxylic ester function, in particular with additional        use of an initiator, or    -   (B) of at least one Lewis acid suitable as a polymerization        catalyst or of a complex which is effective as a polymerization        catalyst and is formed from at least one Lewis acid and at least        one donor, and in the presence of at least one initiator, using        as the at least one initiator an organic sulfonic acid of the        general formula Z—SO₃H in which the variable Z denotes a C₁- to        C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to        C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇- to        C₂₀-arylalkyl radical,

treating the resulting high-reactivity isobutene homo- or copolymer witha suitable activating agent, especially with chlorine, and then reactingwith n equivalents of ammonia or of a mono- or polyamine.

In a further preferred embodiment, the process according to theinvention for preparing isobutene homo- or copolymer derivatives of thegeneral formula I in which A is a low molecular weight polar group whichcomprises a carboxylic acid derivative function, especially acarboximide function, is performed by polymerizing isobutene or anisobutene-comprising monomer mixture in the presence

-   -   (A) of an iron halide-donor complex effective as a        polymerization catalyst, of an aluminum trihalide-donor complex        or of an alkylaluminum halide-donor complex which comprises, as        the donor, an organic compound with at least one ether function        or a carboxylic ester function, in particular with additional        use of an initiator, or    -   (B) of at least one Lewis acid suitable as a polymerization        catalyst or of a complex which is effective as a polymerization        catalyst and is formed from at least one Lewis acid and at least        one donor, and in the presence of at least one initiator, using        as the at least one initiator an organic sulfonic acid of the        general formula Z—SO₃H in which the variable Z denotes a C₁- to        C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to        C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇- to        C₂₀-arylalkyl radical,

reacting the resulting high-reactivity isobutene homo- or copolymer withan ethylenically unsaturated C₄- to C₁₂-dicarboxylic acid or a reactivederivative thereof, especially with maleic anhydride, thermally or withhalogen catalysis, and optionally subsequently converting the productwith a mono- or polyamine to the corresponding carboxamide orcarboximide derivative, and the resulting carboxamide or carboximidederivative can be modified by further reaction with at least one C₂- toC₁₂-dicarboxylic anhydride, with at least one C₂- to C₄-alkylenecarbonate and/or with boric acid.

In a further preferred embodiment, the process according to theinvention for preparing isobutene homo- or copolymer derivatives of thegeneral formula I in which A is a low molecular weight polar group whichcomprises an amino function is performed by polymerizing isobutene or anisobutene-comprising monomer mixture in the presence

-   -   (A) of an iron halide-donor complex effective as a        polymerization catalyst, of an aluminum trihalide-donor complex        or of an alkylaluminum halide-donor complex which comprises, as        the donor, an organic compound with at least one ether function        or a carboxylic ester function, in particular with additional        use of an initiator, or    -   (B) of at least one Lewis acid suitable as a polymerization        catalyst or of a complex which is effective as a polymerization        catalyst and is formed from at least one Lewis acid and at least        one donor, and in the presence of at least one initiator, using        as the at least one initiator an organic sulfonic acid of the        general formula Z—SO₃H in which the variable Z denotes a C₁- to        C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to        C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇- to        C₂₀-arylalkyl radical,

converting the resulting high-reactivity isobutene homo- or copolymerwith a phenol to the corresponding alkylphenol, and then converting thelatter by reaction with an aldehyde and a primary or secondary amine tothe corresponding Mannich adduct.

The present invention also provides novel isobutene homopolymerderivatives of the general formula II

in which

R¹⁰, R¹¹and R¹² each independently denote hydrogen, C₁- to C₂₀-alkyl,C₅- to C₈-cycloalkyl, C₆- to C₂₀-aryl, C₇- to C₂₀-alkylaryl or phenyl,where any aromatic ring may also bear one or more C₁- to C₄-alkyl or C₁-to C₄-alkoxy radicals or moieties of the general formula III

as substituents, where not more than one of the variables R¹⁰, R¹¹ andR¹² is hydrogen and at least one of the variables R¹⁰, R¹¹ and R¹² isphenyl which may also bear one or more C₁- to C₄-alkyl or C₁ toC₄-alkoxy radicals or one or two moieties of the general formula III assubstituents,

Y is an isobutylene or an isobutenylene bridge unit,

A is a low molecular weight polar group which comprises one or moreamino functions and/or nitro groups and/or hydroxyl groups and/orcarboxylic acid or carboxylic acid derivative functions, especiallysuccinic anhydride or succinic acid derivative functions, and/orsulfonic acid or sulfonic acid derivative functions and/or aldehydefunctions and/or silyl groups,

y is from 1 to 350, especially from 9 to 100, in particular from 12 to50, where the two or three variables y in the molecule in the case oftelechelic isobutene homopolymer derivatives II may be the same ordifferent, and

z is 0 or preferably 1.

The isobutene homo- and copolymer derivatives prepared in accordancewith the invention are suitable, for example, as fuel and lubricantadditives.

The isobutene homo- or copolymer derivatives prepared in accordance withthe invention are prepared from isobutene polymers having a high contentof terminal vinylidene double bonds, which is usually much higher than90 mol %, and can thus be obtained in high yields. In addition,appearance and consistency of these derivatives, for example the colorthereof, are improved. In addition, the physical properties of thesederivatives, especially the viscosity behavior at low temperatures, andthe solubilities, especially in polar media, the thermal stability andthe storage stability of the derivatives are also improved. The catalystsystem used to obtain isobutene polymers in the precursor issufficiently active, long-lived, unproblematic to handle and notsusceptible to faults, and more particularly is free of fluorine; thus,unwanted corrosion caused by the residual fluorine content on metallicmaterials and steel types is avoided.

1. A process for preparing isobutene homo- or copolymer derivatives ofthe general formula IPOL(-A)_(n)   (I) in which POL denotes the n-functional radical of ahydrophobic polyisobutene homo- or copolymer which has a number-averagemolecular weight (M_(n)) of 110 to 250 000 and may comprise incorporatedstructural units formed from mono-, di- or trifunctional initiators, Ais a low molecular weight polar group which in each case comprises oneor more amino functions and/or nitro groups and/or hydroxyl groupsand/or mercaptan groups and/or carboxylic acid or carboxylic acidderivative functions, especially succinic anhydride or succinic acidderivative functions, and/or sulfonic acid or sulfonic acid derivativefunctions and/or aldehyde functions and/or silyl groups, and thevariable n is 1, 2 or 3, where the variables A may be the same ordifferent when n=2 and n=3, which comprises polymerizing isobutene or anisobutene-comprising monomer mixture in the presence (A) of an ironhalide-donor complex effective as a polymerization catalyst, of analuminum trihalide-donor complex or of an alkylaluminum halide-donorcomplex which comprises, as the donor, an organic compound with at leastone ether function or a carboxylic ester function, or (B) of at leastone Lewis acid suitable as a polymerization catalyst or of a complexwhich is effective as a polymerization catalyst and is formed from atleast one Lewis acid and at least one donor, and in the presence of atleast one initiator, using as the at least one initiator an organicsulfonic acid of the general formula Z—SO₃H in which the variable Zdenotes a C₁- to C₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- toC₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇- to C₂₀-arylalkylradical, reacting the resulting high-reactivity isobutene homo- orcopolymer which has a content of at least 50 mol % of terminalvinylidene double bonds per polyisobutene chain end with at least nequivalents of a compound which introduces the low molecular weightpolar A group or a substructure of the low molecular weight polar Agroup and, in the case of reaction with a substructure, completing theformation of the low molecular weight polar A group by furtherreactions.
 2. The process according to claim 1, wherein isobutene or anisobutene-comprising monomer mixture is polymerized according toembodiment (A) in the presence of an iron chloride-donor complex oraluminum trichloride-donor complex effective as a polymerizationcatalyst.
 3. The process according to claim 1 or 2, wherein thepolymerization catalyst used according to embodiment (A) is an ironhalide-donor complex, an aluminum trihalide-donor complex or analkylaluminum halide-donor complex comprising, as the donor, adihydrocarbyl ether of the general formula R¹—O—R² in which thevariables R¹ and R² are each independently C₁- to C₂₀-alkyl radicals,C₅- to C₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals or C₇- toC₂₀-arylalkyl radicals.
 4. The process according to claim 1 or 2,wherein the polymerization catalyst used according to embodiment (A) isan iron halide-donor complex, an aluminum trihalide-donor complex or analkylaluminum halide-donor complex comprising, as the donor, ahydrocarbyl carboxylate of the general formula R³—COOR⁴ in which thevariables R³ and R⁴ are each independently C₁- to C₂₀-alkyl radicals,C₅- to C₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals or C₇- toC₂₀-arylalkyl radicals.
 5. The process according to claims 1 to 4,wherein the polymerization catalyst used according to embodiment (A) isan iron halide-donor complex, an aluminum trihalide-donor complex or analkylaluminum halide-donor complex, in which the donor compound has atotal carbon number of 3 to
 16. 6. The process according to claims 1 to5, wherein the polymerization is performed according to embodiment (A)with additional use of an initiator which is selected from organichydroxyl compounds in which one or more hydroxyl groups are each bondedto an sp³-hybridized carbon atom or to an aromatic ring, organic halogencompounds, in which one or more halogen atoms are each bonded to ansp³-hybridized carbon atom, protic acids and water.
 7. The processaccording to claim 6, wherein the initiator is selected from water, oneor more protic acids, methanol, ethanol, 1-phenylethanol,1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol,2-phenyl-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol,1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chlorideand 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)benzene and mixturesthereof.
 8. The process according to claims 1 to 7, wherein thepolymerization is performed according to embodiment (A) in the presenceof 0.01 to 10 mmol, based in each case on 1 mol of isobutene monomerused in the case of homopolymerization of isobutene or on 1 mol of thetotal amount of the polymerizable monomers used in the case ofcopolymerization of isobutene, of a basic nitrogen compound.
 9. Theprocess according to claim 8, wherein the basic nitrogen compound usedis pyridine or a derivative of pyridine.
 10. The process according toclaims 1 to 9, wherein the polymerization is performed according toembodiment (A) in a halogenated aliphatic hydrocarbon or in a mixture ofhalogenated aliphatic hydrocarbons or in a mixture of at least onehalogenated aliphatic hydrocarbon and at least one aliphatic,cycloaliphatic or aromatic hydrocarbon or in a halogen-free aliphatic orhalogen-free aromatic hydrocarbon as an inert diluent.
 11. The processaccording to claim 1, wherein, according to embodiment (B), the at leastone initiator used is an organic sulfonic acid selected frommethanesulfonic acid, trifluoromethanesulfonic acid,trichloromethanesulfonic acid and toluenesulfonic acid, or mixturesthereof.
 12. The process according to claim 1 or 11, wherein, accordingto embodiment (B), the Lewis acid used for the complex effective as apolymerization catalyst is at least one compound selected from thebinary chlorine and fluorine compounds of the elements of transitiongroups 1 to 8 and main groups 3 to 5 of the Periodic Table or mixturesthereof.
 13. The process according to claim 12, wherein the Lewis acidused is a binary chlorine or fluorine compound selected from BCl₃,AlCl₃, TiCl₄, FeCl₂, FeCl₃, ZnCl₂, BF₃, AlF₃, TiF₄, FeF₂, FeF₃ and ZnF₂thereof.
 14. The process according to claims 1, 11, 12 and 13, wherein,according to embodiment (B), a complex which is effective as apolymerization catalyst and comprises, as a donor, an organic compoundwith at least one ether function or a carboxylic ester function is used.15. The process according to claim 14, wherein the organic compoundwhich functions as the donor is a dihydrocarbyl ether of the generalformula R¹—O—R², in which the variables R¹ and R² each independentlydenote C₁- to C₂₀-alkyl radicals, C₅- to C₈-cycloalkyl radicals, C₅- toC₂₀-aryl radicals or C₇- to C₂₀-arylalkyl radicals, or a hydrocarbylcarboxylate of the general formula R³—COOR⁴, in which the variables R³and R⁴ each independently denote C₁- to C₂₀-alkyl radicals, C₅- toC₈-cycloalkyl radicals, C₆- to C₂₀-aryl radicals or C₇- to C₂₀arylalkylradicals.
 16. The process according to claim 15, wherein the organiccompound which functions as the donor has a total carbon number of 3 to16.
 17. The process according to claims 1, 11, 12, 13, 14, 15 and 16,wherein, according to embodiment (B), the polymerization is performedwith additional use of at least one further initiator which is mono- orpolyfunctional and is selected from organic hydroxyl compounds, organichalogen compounds, protic acids and water.
 18. The process according toclaim 17, wherein the at least one additional initiator is selected fromwater, one or more protic acids, methanol, ethanol, 1-phenylethanol,1-(p-methoxyphenyl)ethanol, n-propanol, isopropanol,2-phenyl-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol,1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chlorideand 1,3- or 1,4-bis(1-hydroxy-1-methylethyl)-benzene, and mixturesthereof.
 19. The process according to claims 1, 11, 12, 13, 14, 15, 16,17 and 18, wherein, according to embodiment (B), the polymerization isperformed in the presence of 0.01 to 10 mmol, based in each case on 1mol of isobutene monomer used in the case of homopolymerization ofisobutene or on 1 mol of the total amount of the polymerizable monomersused in the case of copolymerization of isobutene, of a basic nitrogencompound.
 20. The process according to claim 19, wherein the basicnitrogen compound used is pyridine or a derivative of pyridine.
 21. Theprocess according to claims 1, 11, 12, 13, 14, 15, 16, 17, 18, 19 and20, wherein, according to embodiment (B), the polymerization isperformed at a temperature of −30° C. to +50° C.
 22. The processaccording to claims 1, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21,wherein, according to embodiment (B), the polymerization is performed inan aliphatic, cycloaliphatic or aromatic hydrocarbon, in a halogenatedaliphatic hydrocarbon or in a mixture of aliphatic, cycloaliphaticand/or aromatic hydrocarbons or from halogenated aliphatic hydrocarbonsor in a mixture of at least one halogenated aliphatic hydrocarbon and atleast one aliphatic, cycloaliphatic or aromatic hydrocarbon as an inertdiluent.
 23. The process according to claims 1 to 22, wherein themonomer source used for the polymerization is a technical C₄ hydrocarbonstream having an isobutene content of 1 to 100% by weight, especially araffinate 1 stream, a b/b stream from an FCC refinery unit, a productstream from a propylene-isobutane cooxidation or a product stream from ametathesis unit.
 24. The process according to claims 1 to 23 forpreparing isobutene homo- or copolymer derivatives of the generalformula I, in which the parent hydrophobic n-functional radical of thePOL has been formed by homopolymerizing isobutene or copolymerizingisobutene with up to 20% by weight of n-butene, is monofunctional andhas a number-average molecular weight (Ma) of 500 to
 5000. 25. Theprocess according to claims 1 to 23 for preparing isobutene homo- orcopolymer derivatives of the general formula I, in which the parenthydrophobic n-functional radical of the POL has been formed byhomopolymerizing isobutene or copolymerizing isobutene with up to 20% byweight of n-butene, in each case with additional use of a di- ortrifunctional initiator (Inifer), is di- or trifunctional and has anumber-average molecular weight (M_(n)) of 500 to 10
 000. 26. Theprocess according to claims 1 to 23 for preparing isobutene copolymerderivatives of the general formula I, in which the parent hydrophobicn-functional radical of the POL has been formed by copolymerizingisobutene with at least one vinylaromatic comonomer, optionally withadditional use of a di- or trifunctional initiator (Inifer), is mono-,di- or trifunctional and has a number-average molecular weight (M_(n))of 500 to 15
 000. 27. The process according to claims 1 to 26 forpreparing isobutene homo- or copolymer derivatives of the generalformula I, in which the low molecular weight polar A group is selectedfrom (a) mono- or polyamino groups having up to 6 nitrogen atoms, whereat least one nitrogen atom has basic properties; (b) nitro groups,optionally in combination with hydroxyl groups; (c) hydroxyl groups,optionally in combination with mono- or polyamino groups, where at leastone nitrogen atom has basic properties; (d) carboxyl groups or thealkali metal or alkaline earth metal salts thereof; (e) sulfo groups orthe alkali metal or alkaline earth metal salts thereof; (f)polyoxy-C₂-C₄-alkylene moieties terminated by hydroxyl groups, mono- orpolyamino groups, where at least one nitrogen atom has basic properties,or by carbamate groups; (g) carboxylic ester groups; (h) succinicanhydride or moieties which are derived from succinic anhydride and havehydroxyl and/or amino and/or quaternized amino and/or amido and/or imidogroups, which have been prepared by thermal or halogen-catalyzedmaleation of the internal double bond(s) and of the terminal vinylidenedouble bond(s) of the parent polyisobutene homo- or copolymers of thePOL with maleic anhydride and, in the case of moieties which are derivedfrom succinic anhydride and have hydroxyl and/or amino and/orquaternized amino and/or amido and/or imido groups, by appropriatefurther reactions, and any resulting carboxamide or carboximidederivative can be modified by further reaction with at least one C₂- toC₁₂-dicarboxylic anhydride, with at least one C₂- to C₄-alkylenecarbonate and/or with boric acid; (j) moieties obtained by Mannichreaction of POL-substituted phenols with aldehydes and mono- orpolyamines; (k) phenol, alkylphenol or (hydroxyalkyl) phenol moieties;(l) hydroxymethyl groups; (m) moieties which have been obtained byepoxidation of the terminal vinylidene double bond(s) of the parentpolyisobutene homo- or copolymers of the POL and subsequent (i)hydrolysis to the 1,2-diol, (ii) reaction with a thiol or a polythiol,(iii) reaction with ammonia, a monoamine or a polyamine, (iv) reactionwith a borane to give a borate ester and oxidative cleavage of theborate ester to the 1,3-diol, (v) conversion to an aldehyde, (vi)conversion to an aldehyde and conversion of the aldehyde to an oxime andreduction of the oxime to the amine, (vii) conversion to an aldehyde andconversion of the aldehyde to an azomethine cation and hydrolysis to theamine, (viii) conversion to an aldehyde and conversion of the aldehydeto an alcohol or (ix) conversion to an aldehyde and conversion of thealdehyde to a Schiff base or an enamine, and reduction of the Schiffbase or of the enamine to the amine; (n) moieties which have beenobtained by hydroboration of the terminal vinylidene double bond(s) ofthe parent polyisobutene homo- or copolymers of the POL and subsequentoxidation of the primary hydroboration product; and (o) moieties whichhave been obtained by hydrosilylation of the terminal vinylidene doublebond(s) of the parent polyisobutene homo- or copolymers of the POL. 28.A process for preparing isobutene homo- or copolymer derivatives of thegeneral formula I in which A is a low molecular weight polar group whichcomprises an amino function according to claims 1 to 27, which comprisespolymerizing isobutene or an isobutene-comprising monomer mixture in thepresence (A) of an iron halide-donor complex effective as apolymerization catalyst, of an aluminum trihalide-donor complex or of analkylaluminum halide-donor complex which comprises, as the donor, anorganic compound with at least one ether function or a carboxylic esterfunction, in particular with additional use of an initiator, or (B) ofat least one Lewis acid suitable as a polymerization catalyst or of acomplex which is effective as a polymerization catalyst and is formedfrom at least one Lewis acid and at least one donor, and in the presenceof at least one initiator, using as the at least one initiator anorganic sulfonic acid of the general formula Z—SO₃H in which thevariable Z denotes a C₁- to C₂₀-alkyl radical, C₁- to C₂₀-haloalkylradical, C₅- to C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇-to C₂₀-arylalkyl radical, hydroformylating the resulting high-reactivityisobutene homo- or copolymer with a suitable catalyst in the presence ofcarbon monoxide and hydrogen, and then reductively aminating in thepresence of at least n equivalents of ammonia or of a mono- orpolyamine.
 29. A process for preparing isobutene homo- or copolymerderivatives of the general formula I in which A is a low molecularweight polar group which comprises an amino function according to claims1 to 27, which comprises polymerizing isobutene or anisobutene-comprising monomer mixture in the presence (A) of an ironhalide-donor complex effective as a polymerization catalyst, of analuminum trihalide-donor complex or of an alkylaluminum halide-donorcomplex which comprises, as the donor, an organic compound with at leastone ether function or a carboxylic ester function, in particular withadditional use of an initiator, or (B) of at least one Lewis acidsuitable as a polymerization catalyst or of a complex which is effectiveas a polymerization catalyst and is formed from at least one Lewis acidand at least one donor, and in the presence of at least one initiator,using as the at least one initiator an organic sulfonic acid of thegeneral formula Z—SO₃H in which the variable Z denotes a C₁- toC₂₀-alkyl radical, C₁- to C₂₀-haloalkyl radical, C₅- to C₈-cycloalkylradical, C₆- to C₂₀-aryl radical or a C₇- to C₂₀-arylalkyl radical,treating the resulting high-reactivity isobutene homo- or copolymer witha suitable activating agent, especially with chlorine, and then reactingwith n equivalents of ammonia or of a mono- or polyamine.
 30. A processfor preparing isobutene homo- or copolymer derivatives of the generalformula I in which A is a low molecular weight polar group whichcomprises a carboxylic acid derivative function, especially acarboximide function, according to claims 1 to 27, which comprisespolymerizing isobutene or an isobutene-comprising monomer mixture in thepresence (A) of an iron halide-donor complex effective as apolymerization catalyst, of an aluminum trihalide-donor complex or of analkylaluminum halide-donor complex which comprises, as the donor, anorganic compound with at least one ether function or a carboxylic esterfunction, in particular with additional use of an initiator, or (B) ofat least one Lewis acid suitable as a polymerization catalyst or of acomplex which is effective as a polymerization catalyst and is formedfrom at least one Lewis acid and at least one donor, and in the presenceof at least one initiator, using as the at least one initiator anorganic sulfonic acid of the general formula Z—SO₃H in which thevariable Z denotes a C₁- to C₂₀-alkyl radical, C₁- to C₂₀-haloalkylradical, C₅- to C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇-to C₂₀-arylalkyl radical, reacting the resulting high-reactivityisobutene homo- or copolymer with an ethylenically unsaturated C₄- toC₁₂-dicarboxylic acid or a reactive derivative thereof, especially withmaleic anhydride, thermally or with halogen catalysis, and optionallysubsequently converting the product with a mono- or polyamine to thecorresponding carboxamide or carboximide derivative, and the resultingcarboxamide or carboximide derivative can be modified by furtherreaction with at least one C₂- to C₁₂-dicarboxylic anhydride, with atleast one C₂- to C₄-alkylene carbonate and/or with boric acid.
 31. Aprocess for preparing isobutene homo- or copolymer derivatives of thegeneral formula I in which A is a low molecular weight polar group whichcomprises an amino function according to claims 1 to 27, which comprisespolymerizing isobutene or an isobutene-comprising monomer mixture in thepresence (A) of an iron halide-donor complex effective as apolymerization catalyst, of an aluminum trihalide-donor complex or of analkylaluminum halide-donor complex which comprises, as the donor, anorganic compound with at least one ether function or a carboxylic esterfunction, in particular with additional use of an initiator, or (B) ofat least one Lewis acid suitable as a polymerization catalyst or of acomplex which is effective as a polymerization catalyst and is formedfrom at least one Lewis acid and at least one donor, and in the presenceof at least one initiator, using as the at least one initiator anorganic sulfonic acid of the general formula Z—SO₃H in which thevariable Z denotes a C₁ to C₂₀-alkyl radical, C₁- to C₂₀-haloalkylradical, C₆- to C₈-cycloalkyl radical, C₆- to C₂₀-aryl radical or a C₇-to C₂₀-arylalkyl radical, converting the resulting high-reactivityisobutene homo- or copolymer with a phenol to the correspondingalkylphenol, and then converting the latter by reaction with an aldehydeand a primary or secondary amine to the corresponding Mannich adduct.32. An isobutene homopolymer derivative of the general formula II

in which R¹⁰, R¹¹ and R¹² each independently denote hydrogen, C₁- toC₂₀-alkyl, C₅- to C₈-cycloalkyl, C₆- to C₂₀-aryl, C₇- to C₂₀-alkylarylor phenyl, where any aromatic ring may also bear one or more C₁- toC₄-alkyl or C₁- to C₄-alkoxy radicals or moieties of the general formulaIII

as substituents, where not more than one of the variables R¹⁰, R¹¹ andR¹² is hydrogen and at least one of the variables R¹⁰, R¹¹ and R¹² isphenyl which may also bear one or more C₁- to C₄-alkyl or C₁- toC₄-alkoxy radicals or one or two moieties of the general formula III assubstituents, Y is an isobutylene or an isobutenylene bridge unit, A isa low molecular weight polar group which comprises one or more aminofunctions and/or nitro groups and/or hydroxyl groups and/or carboxylicacid or carboxylic acid derivative functions, especially succinicanhydride or succinic acid derivative functions, and/or sulfonic acid orsulfonic acid derivative functions and/or aldehyde functions and/orsilyl groups, y is from 1 to 350, where the two or three variables y inthe molecule in the case of telechelic isobutene homopolymer derivativesII may be the same or different, and z is 0 or 1.